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A couple of points:
Didn't we decide that instead of using:
 openlog(ident[, logopt[, facility]])
we'd use:
 openlog(ident, logopt=None, facility=None)
(or whatever the defaults are)? I can't find a reference, but the argument was that it's how Python signatures are written, so it's clearer if they're all written this way.
You should add some comments to syslog_get_argv explaining why you're handling errors the way you are. That is, why you're swallowing exceptions and continuing. Similarly with the call to PyTuple_New(0).
I also think it would be clearer if using the string "python" were inside syslog_get_argv, but that's a style thing.
Should the fallback be "python", or derived from C's argv[0]?
Is it possible that sys.argv[0] would be unicode?
Is SEP correct, or should it really be using os.path.sep and/or os.path.altsep? This is probably a nit, but I could see it being a problem under cygwin (which I haven't tested yet).
Your "if" statements shouldn't all be on one line. The single-line style with braces isn't used anywhere else in this module, and it's not in the Python code base that I could see (except for the occasional macro).
The example code has some extra spaces around the equal signs. It should be:
 syslog.openlog(logopt=syslog.LOG_PID, facility=syslog.LOG_MAIL)
Thanks for doing this!