"Supported" doesn't necessarily mean it works, and "not supported" does not necessarily mean it doesn't work. Instead, when folks who write software say they support a platform, it means that they have tested the software on that platform and will accept bug reports related to failure to work on that platform.
Using the software on platforms that are "not supported" means you're using them at your own risk. (Of course, free software is generally always used at your own risk.)
For the specific case of 64-bit Windows, I would expect Mono to work in 32-bit mode, but I haven't investigated. It's not just a matter of having an x64 code generator; the ABI for 64-bit Linux differs from 64-bit Windows, the exception handling mechanisms are different, etc.