Yes, you would have to write a custom PHP extension in C/C++ to do the Win32 calls necessary to get a list of users. Or, an easier way would be to write an ISAPI extension (since by definition it's NT only) that your page can call to retrieve user names.
The calls you need to make are "Net*()" calls in Win32. These control access to the SAM for management of user accounts and local/global groups.
Dave
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