Do you have the source for the library? If so, and you recompile it, you might get away with it (as long as the writers of the library didn't make any assumptions that are broken when compiling for x86-64). Test hard, and test long.
If you don't have the source (you just have an i386 compiled binary), the linker won't even let you link x86-64 code to it. The ABIs just aren't compatible.
In the second case, you'll have to create a separate 32-bit helper/wrapper process that links to the 32-bit library, and takes requests to call the library from the 64-bit process through an IPC mechanism (returning the results). You can create wrapper functions on the 64-bit side around the IPC so that it looks like normal calls to the library. Your 64-bit process will have to kick off the 32-bit helper process when it starts up (and make sure the helper process knows to exit when the parent process disappears).