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Where would the paths be located? There exists something like files system redirection in Windows VISTA and higher which will redirect certain paths like C:\Windows\System32 or C:\Program Files and C:\Program Files (x86) to whatever the kernel considers the appropriate location for the current application based on its bitness. So eventhough you ask for C:\Windows\System32 in a 32 bit process, it will be directed to C:\Windows\SysWOW64 when run on a 64 bit OS! It's possible that LabVIEW attempts to be smart when trying to reference a DLL that is defined in the Call Library Node but won't second guess Windows decision when you define the dynamic path.

LabVIEW 32 bit can only load 32 bit dlls regardless of your platform bitness - although you can't install LabVIEWx64 on Win32. You don't need two computers, you need two LabVIEW versions to compile both 32 and 64 bit executables that will then use the 32 and 64 bit dll respectively. That's why we use the conditional disable because only the end developers' (not the end users') bitness counts for when they compile the executable. Bottom line: Executables are either 64 OR 32 bit and each can only use the corresponding DLLs.of that bitness For the OP. I expect the paths are not what you're expecting them to be or you are missing some dependencies of the DLL.