All of them! Compiler, linker, all dependent libraries, etc.
Seriously, this is not a task for the faint-hearted... unless you know what you're doing or are prepared to spend a lot of time learning and following documents like LFS (as Noway2 mentioned), you would be much better off installing a 64-bit system in the first place, or using a LiveCD as BBB suggested.
It is far too complicated for someone to describe how to set up a cross-compilation environment in a few forum posts here. I wouldn't attempt it myself unless the target platform was something that I couldn't install Linux on already.
Annihilannic.