I know both, and from my experience I think Python is a lot cleaner and more flexible...
PHP is good for rapidly making a simple website, but nowadays personally I seem to find myself even web programming in Python do to it's smooth complete nature...
But PHP does have a pretty good marketplace going on,
and is what I normally work in do to availability, even though I prefer Python...
IMO I would go with what ever jobs look the funnest and pay best..
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