I don't know about syslinux, since my syslinux menu is only set for BIOS boot... but
A WinPE3 (Windows 7) can deploy Windows 8... well probably... but you need to copy in the DISM.exe from Win8 or WinPE4. Then again, your other question, YES WinPE4 can deploy Windows 7 no problem.
For UEFI, the WinPE you make must be 64bit version!
Regarding GPT disk, You can do GPT on a UEFI boot (of course) but you can only do a MBR disk if your deployment has the OS on the first partition (BCDBoot might not work). I don't think there is a problem using GPT every time tho, even on disks that are less than 2TB.
So wait, i use tftpd32, how can i make uefi boot into UEFI pxe boot menu? ok perhaps no one is able to yet. so moving on..
Yes I already have a running x64 Win7PE (bios boot via syslinux pxeboot menu) that installs windows 7 x64 all well and fine.
So it's ideal if i can boot into win7pe x64 via legacy pxe and later on set uefi boot..
Right now, I wish to switch to Win7 x64 UEFI+MBR. By default, a 100MB partition is created... i have a hack that makes it so that it doesnt' create this 100MB partition.. if this is helpful info.. So what do I actually need now? Can I install win7 x64 as normal and then set as UEFI later on?