On 2 June 2014, James was named in Colombia's 23-man squad for the 2014 FIFA World Cup and assigned the number 10 shirt.
In the team's opening match of the tournament, James set up the first two goals, scored a last-minute goal with a low shot to seal a 3–0 victory over Greece and was named man of the match by FIFA.
In the second match, James continued his form by scoring with a header and setting up a second goal for Juan Fernando Quintero in a 2–1 victory over Ivory Coast and was once again elected as man of the match.
In the final group stage match against Japan, James came on as a second-half substitute and assisted two Jackson Martínez goals before scoring the final goal in a 4–1 victory.
At the end of the group stage, James was ranked as the best performing player at the tournament by FIFA.

On 28 June, James scored both goals to defeat Uruguay 2–0 at the Maracanã in the round of 16, taking Colombia to its first ever World Cup quarter-finals.
These goals made him the first player to score in all of his team's opening matches since Ronaldo and Rivaldo in 2002.
His volleyed opening goal was described as "one of the greatest goals the World Cup has ever seen" by opposing manager Óscar Tabárez, who also called James "the best player in the World Cup."
Because of his performance against the Uruguayans, James was named by FIFA as man of the match for the third time in four matches.
The volley was later voted as the best goal in the tournament by more than four million people on FIFA's website and won the FIFA Puskás Award for the best goal of the year.
In the quarter-final against Brazil, he scored his sixth goal of the tournament, a penalty in Colombia's 2–1 defeat.

A tearful James was consoled by Brazil's David Luiz and stated, "He (David) told me I was a good player.
The truth is that having so many superstars hug me did make me happy.
We have to raise our heads now and thank Colombia for their support.
We are sad because we wanted to keep going and set new records.
We gave everything to reach the semi-final, but we have to be proud because we played a great side.
I'm crying because we gave everything.
We're sad but we also have to feel proud because we left our skin out there."
Luiz and Rodríguez also exchanged jerseys.
James received a standing ovation from the home crowd, ending his first World Cup campaign with six goals and two assists in five matches.
On 11 July, he was named on the 10-man shortlist for FIFA's Golden Ball award for the tournament's best player.
He then won the Golden Boot as the tournament's top goalscorer despite being eliminated in the quarter finals.
Due to his performances, he was named in the World Cup All Star XI and was also listed in the Cup's star XI by Castrol's index rating system in FIFA's website.
Argentina legend Diego Maradona argued that James, rather than Lionel Messi, that should have won the tournament's Golden Ball award.
On 2 June 2014, James was named in Colombia's 23-man squad for the 2014 FIFA World Cup and assigned the number 10 shirt. In the team's opening match of the tournament, James set up the first two goals, scored a last-minute goal with a low shot to seal a 3–0 victory over Greece and was named man of the match by FIFA. In the second match, James continued his form by scoring with a header and setting up a second goal for Juan Fernando Quintero in a 2–1 victory over Ivory Coast and was once again elected as man of the match. In the final group stage match against Japan, James came on as a second-half substitute and assisted two Jackson Martínez goals before scoring the final goal in a 4–1 victory. At the end of the group stage, James was ranked as the best performing player at the tournament by FIFA.
On 28 June, James scored both goals to defeat Uruguay 2–0 at the Maracanã in the round of 16, taking Colombia to its first ever World Cup quarter-finals. These goals made him the first player to score in all of his team's opening matches since Ronaldo and Rivaldo in 2002. His volleyed opening goal was described as "one of the greatest goals the World Cup has ever seen" by opposing manager Óscar Tabárez, who also called James "the best player in the World Cup." Because of his performance against the Uruguayans, James was named by FIFA as man of the match for the third time in four matches. The volley was later voted as the best goal in the tournament by more than four million people on FIFA's website and won the FIFA Puskás Award for the best goal of the year. In the quarter-final against Brazil, he scored his sixth goal of the tournament, a penalty in Colombia's 2–1 defeat.
A tearful James was consoled by Brazil's David Luiz and stated, "He (David) told me I was a good player. The truth is that having so many superstars hug me did make me happy. We have to raise our heads now and thank Colombia for their support. We are sad because we wanted to keep going and set new records. We gave everything to reach the semi-final, but we have to be proud because we played a great side. I'm crying because we gave everything. We're sad but we also have to feel proud because we left our skin out there." Luiz and Rodríguez also exchanged jerseys. James received a standing ovation from the home crowd, ending his first World Cup campaign with six goals and two assists in five matches. On 11 July, he was named on the 10-man shortlist for FIFA's Golden Ball award for the tournament's best player. He then won the Golden Boot as the tournament's top goalscorer despite being eliminated in the quarter finals. Due to his performances, he was named in the World Cup All Star XI and was also listed in the Cup's star XI by Castrol's index rating system in FIFA's website. Argentina legend Diego Maradona argued that James, rather than Lionel Messi, that should have won the tournament's Golden Ball award.
James Rodríguez