I was thinking of rewriting my custom PHP app on a framework... mainly for the solidity and more ease of growth going forward.  Right now its a pseudo MVC setup with lots of hacks in between.
I already have the db built out and the app uses a lot of AJAX too.
I am not concerned with the amount of work involved as the solidity of the platform I move things to.  Server configurations are no worries.  I am also looking to increase performance all around.  
My friend (and Python enthusiast) told me things of python rendering tabular type data at almost 40% increase over PHP and speed is definitely a decision maker in this.
Taking out the fact that there would be significantly less work moving to a PHP based framework since the app is PHP already which would be the best fit?
I know there are a lot of PHP vs Python stories out there.  Python seems to be the clear winner, but how easy is it to use with standard web stuff like AJAX?
I just want to know who would use which and why vs the other.
Which language do you prefer?  That's all that really matters.  Both have solid frameworks and similar performance. If you want to increase performance, writing more efficient code is going to make a way bigger difference.
Personally, I like python.  Django is great, but you might also consider Flask or Pyramid/Pylons.  Ajax is just as easy with python as it is with PHP--it's only a request. The server configuration is definitely harder--it doesn't get any easier than PHP--but it's not that hard, and you said you didn't mind it.  If you like both languages equally, give python a shot.
Rewriting A Custom PHP App on a framework. Torn between Python (Django) and PHP (CodeIgniter)