On January 4, 2007, Webb was sworn into the 110th U.S. Senate, accompanied by Sen. John Warner, R-Va.,
a fellow former Secretary of the Navy; and former Virginia Democratic Sen. Chuck Robb, who held the same seat before losing to Allen.

On his first day in the Senate, Webb introduced the Post-9/11 Veterans Educational Assistance Act, to expand benefits for military families, which he had written.
The act replaces key provisions of the Montgomery G.I. Bill for recent veterans and "makes veterans benefits identical to those soldiers received following World War II". "
With many of our military members serving two or three tours of duty in Iraq and Afghanistan, it is past time to enact a new veterans' education program modeled on the World War II era G.I. bill.
This is exactly what our legislation does", Webb said.
It became law on June 30, 2008, as part of the Supplemental Appropriations Act of 2008.

In a January 4, 2007, appearance on The Situation Room, Webb articulated his position on the Iraq War:
What we really need to do is to get into the arena where we can talk about a strategy, talk about the pluses and the minuses of the Baker-Hamilton Commission and work toward a solution that, on the one hand, will allow us to remove our combat troops, but on the other, will increase the stability of the region, allow us to continue to fight against international terrorism and allow us, as a nation, to address our strategic interests around the world.
And this is – this is one of the drawbacks that we've had with so many troops having been put into this constant rotational basis inside one country when we have a war against international terrorism that's global.

Asked by Wolf Blitzer if he would ever support the efforts of Dennis Kucinich to cut funding for the war, Webb said,
I – you know, I lived through Vietnam.
I lived through it as a Marine and I know that those sorts of approaches, while they seem attractive on one level are really not that realistic.
What we want to do – and I was talking with a number of senators today – is to try to get some of these so-called emergency legislation packages back into the committee process so that the committees can actually play.

On January 23, 2007, Webb delivered the Democratic response to the President's State of the Union address, focusing on the economy and Iraq.
Webb's speech drew positive reviews, and was regarded as one of the stronger State of the Union responses in recent memory.

On March 5, 2007, Webb introduced his second piece of legislation, S. 759, intended to prohibit the use of funds for military operations in Iran without the prior approval of Congress.
In a statement on the floor of the Senate, Webb said, "The major function of this legislation is to prevent this Administration from commencing unprovoked military activities against Iran without the approval of the Congress.
The legislation accomplishes this goal through the proper constitutional process of prohibiting all funding for such an endeavor."


On March 26, 2007, a senatorial aide of Webb, Phillip Thompson, was arrested for carrying Webb's loaded pistol as he entered the Russell Senate Office Building and for carrying unregistered ammunition.
The weapon was discovered when Thompson went through an X-ray machine with a briefcase that contained a loaded pistol and two additional loaded magazines.
Charges against the aide were dismissed after prosecutors concluded it could not be proved beyond a reasonable doubt that Thompson was aware that the gun and ammunition were in the briefcase.
Webb responded to his aide's arrest by reiterating his support for gun-owners' rights:
I'm a strong supporter of the Second Amendment; I have had a permit to carry a weapon in Virginia for a long time; I believe that it's important; it's important to me personally and to a lot of people in the situation that I'm in to be able to defend myself and my family.
On January 4, 2007, Webb was sworn into the 110th U.S. Senate, accompanied by Sen. John Warner, R-Va., a fellow former Secretary of the Navy; and former Virginia Democratic Sen. Chuck Robb, who held the same seat before losing to Allen.
On his first day in the Senate, Webb introduced the Post-9/11 Veterans Educational Assistance Act, to expand benefits for military families, which he had written. The act replaces key provisions of the Montgomery G.I. Bill for recent veterans and "makes veterans benefits identical to those soldiers received following World War II". "With many of our military members serving two or three tours of duty in Iraq and Afghanistan, it is past time to enact a new veterans' education program modeled on the World War II era G.I. bill. This is exactly what our legislation does", Webb said. It became law on June 30, 2008, as part of the Supplemental Appropriations Act of 2008.
In a January 4, 2007, appearance on The Situation Room, Webb articulated his position on the Iraq War:
What we really need to do is to get into the arena where we can talk about a strategy, talk about the pluses and the minuses of the Baker-Hamilton Commission and work toward a solution that, on the one hand, will allow us to remove our combat troops, but on the other, will increase the stability of the region, allow us to continue to fight against international terrorism and allow us, as a nation, to address our strategic interests around the world. And this is – this is one of the drawbacks that we've had with so many troops having been put into this constant rotational basis inside one country when we have a war against international terrorism that's global.
Asked by Wolf Blitzer if he would ever support the efforts of Dennis Kucinich to cut funding for the war, Webb said,
I – you know, I lived through Vietnam. I lived through it as a Marine and I know that those sorts of approaches, while they seem attractive on one level are really not that realistic. What we want to do – and I was talking with a number of senators today – is to try to get some of these so-called emergency legislation packages back into the committee process so that the committees can actually play.
On January 23, 2007, Webb delivered the Democratic response to the President's State of the Union address, focusing on the economy and Iraq. Webb's speech drew positive reviews, and was regarded as one of the stronger State of the Union responses in recent memory.
On March 5, 2007, Webb introduced his second piece of legislation, S. 759, intended to prohibit the use of funds for military operations in Iran without the prior approval of Congress. In a statement on the floor of the Senate, Webb said, "The major function of this legislation is to prevent this Administration from commencing unprovoked military activities against Iran without the approval of the Congress. The legislation accomplishes this goal through the proper constitutional process of prohibiting all funding for such an endeavor."

On March 26, 2007, a senatorial aide of Webb, Phillip Thompson, was arrested for carrying Webb's loaded pistol as he entered the Russell Senate Office Building and for carrying unregistered ammunition. The weapon was discovered when Thompson went through an X-ray machine with a briefcase that contained a loaded pistol and two additional loaded magazines. Charges against the aide were dismissed after prosecutors concluded it could not be proved beyond a reasonable doubt that Thompson was aware that the gun and ammunition were in the briefcase. Webb responded to his aide's arrest by reiterating his support for gun-owners' rights:
I'm a strong supporter of the Second Amendment; I have had a permit to carry a weapon in Virginia for a long time; I believe that it's important; it's important to me personally and to a lot of people in the situation that I'm in to be able to defend myself and my family.
Jim Webb