This is not possible because system-wide environment variables are stored in HKLM \ System \ CurrentControlSet \ Control \ Session Manager \ Environment, and there is no WOW64 redirection to the SYSTEM hive.
If your program is installed in Program Files, you can add your path based on% ProgramFiles% to the PATH environment variable -% ProgramFiles% expands to 32-bit program files when working under WOW64.
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