Basically, the answer is no.
If the underlying hardware is 32-bit, then it definitely won't support 64-bit instructions.
If the hardware is 64-bit (and the OS is just 32-bit), it's possible in theory, but would require the kernel to not only setup a 64-bit code segment, but to also setup 64-bit paging (I think). Since I doubt the 32-bit Windows kernel supports either of these, then it's not possible.