You'll need to tell us the exact path and how do you go about constructing it. It can be as simple as the app not using env variable expansion but assuming that user's folders are where they were before.
Path virtualization (there are 2 kids actually) that people mentioned will hit you only if your app is trying to mess with system folders.
More puzzling problem will hit you if you are not expanding env vars like APPDATA, LOCALAPPDATA etc. and not expecting that there's more of them on Win7 and 2k8. Not only that default paths of user's files changed but some of them can also be on network shares - for the same user. So if you were running based on expectation that all user's stuff will be at definite paths under say %USERPROFILE% you can get hit by several surprises. Also notice %ProgramData% .
Fastest way to find out - open cmd.exe, run set and if you see some paths that you are constructing in alternative ways, take notice that you need to start expanding env vars for them. Then open cmd.exe as a 32-bit app and check set again. You can also pick them up via Process Explorer from some running 32-bit or 64-bit app.
Switching your app to 64-bit build will resolve most of virtualization issues but not the env var expansion. Also if your app is touching system folders you need to request elevated run from the code or even better make the manifest and declare it there. Then OS will yell at user up front if his UAC is on and your app will avoid that 2nd virtualization. BTW, virtualization is controllable via group policies so it might be present on some boxes and missing on others.