Q:

Why does James Bond win when he goes all-in in Casino Royale?

In the climax of the poker game, James bets all his money - $40.5 million. In response, Le Chiffre somewhat nervously counters with an all-in of his own - but a substantially higher call. Since Le Chiffre has been bleeding the rest of the table dry all night, he has Bond's amount covered. It's impressive that Bond wins the hand, but why does that immediately end the game?
If I'm not mistaken, this is the sequence of events:

Player 1 bets $5M; pot size is $5M
Player 2 bets $6M; pot size is $11M
Le Chiffre bets $12M; pot size is $23M
Bond bets $40.5M; pot size is $63.5M
Le Chiffre goes all in; pot size is $115M

This implies Le Chiffre still had Bond covered with $11M left over for himself. The game shouldn't have been over. Bond would clearly be hugely advantaged at that point, with $104M to $11M, but Le Chiffre shouldn't have been eliminated immediately, right?

A:

Because Bond had more in the pot than Le Chiffre
The pot in the final game starts at 4 millions since the big blind was 1 million with 4 players.
Then Le Chiffre bets 5 millions and they all follow, raising the pot to 24 millions.

Mathis: Twenty-four million in the pot already.

If you redo your calculations based on that, you'll see that Le Chiffre is actually short of one measly million dollars!
Since indeed the pot reaches 115 millions :
115 =
24 (pot before Le Chiffre's bet) +
5 (all in from guy#1) +
6 (all in from guy#2) +
40.5 (all in from Bond) +
39.5 (by deduction, all in from Le Chiffre, including his 12 million bet)
Edit:
Note that we don't know how Bond ends up having more money than Le Chiffre at the beginning of the last hand even though Le Chiffre dominated the game previously, since we don't see exactly how the game unfolds between Bond's big loss and the last hand. But we can guess:

Bond gets back in the game with a lot of money after his first loss
Bond could have won a lot of smaller hands, allowing him to catch up with Le Chiffre
Other players are eliminated, or in two instances have their resources reduced to 5-6 millions. Bond could have won decisive games against them.

