Currently the only supported platform for x86_64 is EFI.

Building an EFI64 gPXE requires a version of gcc that supports
__attribute__((ms_abi)).  This currently means a development build of
gcc; the feature should be present when gcc 4.4 is released.

In the meantime; you can grab a suitable gcc tree from

  git://git.etherboot.org/scm/people/mcb30/gcc/.git

We have EFI APIs for CPU I/O, PCI I/O, timers, console I/O, user
access and user memory allocation.

EFI executables are created using the vanilla GNU toolchain, with the
EXE header handcrafted in assembly and relocations generated by a
custom efilink utility.