Memory segmentation theortically allows x86-32 to address upto 64 GB of memory (48 bit FAR pointers), BUT it will only work with very specific processors with operating system and application support.
If x86-64 is designed so the memory address translation is always done in 64 bits, then yes, theoretically, it would be possible to use upto 64 GB of memory with x86-32 apps. I would actually imagine this is what they actually do. However the operating system will need to have the memory managment code written in x86-64 to setup the page tables and segment descriptors, otherwise you'll still be limited to 4 GB max.