Windows 32 bits can address a maximum of 3 GB of RAM, no matter how much more there is installed in the machine. So, even though 32-bits applications could theoretically address as much as 4 GB of memory, they're capped to 3 GB by the OS (and even then, there are certain memory pages that are reserved, and other programs run at the same moment, so this maximum can probably never be reached).
However, when running the 64 bits version of Windows, the OS cap is blown away. Does that mean 32-bits applications running through WoW64 can now theoretically access their whole 4 GB address space?