As long as the 64-bit DLL is being loaded by a separate 64-bit process, and all communication between 32-bit process and 64-bit DLL is via loose-coupled IPC-like mechanisms that the OS can marshall, then yes you can do that.
I've done something similar. A 32-bit application needed a custom Print Spooler add-in implemented in a DLL. The app and the spooler add-in communicated via IPC mechanisms (a fancy way of saying temporary files, in this case).
On 64-bit systems everything about the 32-bit application worked fine except that the Print Spooler refused to load the add-in DLL, because the Print Spooler was of course a 64-bit process.
The solution was as simple as rebuilding only the Spooler add-in in 64-bit. No need to change the entire 32-bit app.
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