If Delphi code was written with synchronize to serialize access to the main VCL thread, but this code then is used in a non-VCL application, will it synchronize with the mai
TThread provides facilities for non-VCL programs to check the synchronization queue, so they can continue to use multithreaded libraries that expect to synchronize their methods. This is described in the documentation for CheckSynchronize. Remember that it's the application's job to check the queue, not your library's.
As long as the application honors its part of the contract, your use of Synchronize should be fine. If it doesn't, though, then your program will not work correctly, but I don't know what exact symptoms to expect. Hanging certainly sounds plausible.