The easiest way to check your workstation is to download the VMware Processor Check for 64-Bit Compatibility tool from the VMware website.
You can't run a 64-bit VM session on a 32-bit processor. However, you can run a 64-bit VM session if you have a 64-bit processor but have installed a 32-bit host OS and your processor supports the right extensions. The tool linked above will tell you if yours does.