Introducing Python
I recently introduced Python to my company, which does consulting work for the Post Office.  I did this by waiting until there was a project for which I would be the only programmer, then getting permission to do this new project in Python.  I then did another small project in Python with similarly impressive results.  In addition, I used Python for all of my small throwaway assignments ("can you parse the stats in these files into a CSV file organized by date and site?", etc) and had a quick turnaround time on all of them.
I also evangelized Python a bit; I went out of my way to NOT be obnoxious about it, but I'd occasionally describe why I liked it so much, talked about the personal projects I use it for in my free time and why it's awesome for me, etc.
Eventually we started another project and I convinced everyone to use Python for it.  I took care to point everyone to a lot of documentation, including the specific webpages relating to what they were working on, and every time they had a question, I'd explain how to do things properly by explaining the Pythonic approach to things, etc.
This has worked really well.  However, this might be somewhat different than what you're describing.  In my case I started with moderately small projects and Python is only being used for new projects.  Also, none of my co-workers were really Perl or PHP gurus; they all knew those languages and had been using them for awhile, but it didn't take much effort for them to become more productive in Python than they'd been before.
So if you're talking about new projects with people who currently use PHP but aren't super-experts and don't love that language, then I think switching to Python is a no-brainer.  However, if you're talking about working with a large existing PHP code base with a lot of very experienced PHP programmers who are happy with their current setup, then switching languages is probably not a good idea.  You're probably somewhere in between, so you'll have to weigh the tradeoffs; hopefully my answer will help you do that.
The company I used to work with has two developers working fulltime, and a handful of freelancers. They're in the process of hiring a new lead developer to try to bring order and management to the development.
But, currently, one of the developers has seen the light of Django (the company has only developed in PHP to date) while the other developer is concerned that introducing a new language (Python) is a bad idea right now.
How should they approach introducing this new technology? Obviously with only one of the developers actually knowing Python, there will be no redundancy when that dev is away or leaves the company.
Should they bother to introduce Python, or should they look for PHP-only solutions until such a time when the team actually have more than one Pythonion? Without a team leader, the decisions are having to fall to them.