You will not have a problem returning to Python 2.x after learning Python 3 or vice versa. Too many differences. (Some standard changes to the library, printing is a function, all lines are Unicode - you will never notice most of them).
Actually, if you learn Python 3 now and get to work with Python, you will almost certainly be working with Python 2.x right now. Python 3 has not yet become widespread. However, Python 3 will be more adopted in the near future, as several libraries are ported to Python 3.
If you need to use Matplotlib specifically, then you should use Python 2.7 (it makes no sense to use Python 3 right now if you don't need a library). But learning Python 3 at first will by no means lead you to any flaw and may put you ahead of the curve when most people finally make the switch.
There is also nothing stopping you from using both (Python 3 for learning / experimenting, Python 2.7 for working).
Raffettler
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