The question I get asked most often by people just getting into scripting in Maya is, "Should I learn MEL first or go right to Python?". It's a legitimate question and at this stage in the lives of both languages, it has merit. The reality is you need to learn both...but which one first? And why learn MEL when Python is there? Maya's embedded language has been around for ages and is notoriously weak and difficult to use in certain areas. As Python slithers it's way deeper and deeper into our pipelines, many believe MEL will be phased out completely in coming years. Seeings how it will inevitably become more and more prevalent in 3D applications and is not Maya-specific, isn't it only logical to not bother with Maya's aging language and go right to Python? All signs seem to point that way, but I don't agree with this philosophy and I'll explain why.
First, learn enough MEL for it to be useful and help you work, then start to learn Python along side it.
If you are new to programming and scripting, you are unlikely to learn enough Python quickly enough for it to be of any use to you. Python is definitely more powerful, gives you more control, and is really more fun to use in the end...BUT...it's more difficult. There are more rules, more things involved with getting it working properly and generally just more things you need to know in order to use and learn it. You'll need to learn the basics of installing libraries, having paths set up correctly, using environment variables, linking modules, and all sorts of steps just to get it doing what you want. Of course you can just go in there and start giving it Maya commands, but at that point you're not taking advantage of it's abilities and may as well use MEL. That brings me to my point.
With MEL, you can start doing things almost instantly even with little to no knowledge of how it works. Compared to some languages it's relatively easy to pick up and get going with and it exists in Maya already with great documentation. To get started, you can watch your Script Editor to see what certain commands are doing and how they work. Run a tool or do something in Maya and watch what kind of code it spits out in the Script Editor. Copy and paste that code and start changing things around to make your own little scripts and buttons. Learning the basics of variables, functions and syntax are all easy using the tutorials in the Maya documentation. All in all, within a couple of hours you can be writing small snippets of code that will actually be speeding up your work-flow. It's not to say you can't do the same with Python if you're a fast learner, but generally speaking you'll be up and running with MEL a lot quicker.
Once you're cruising with MEL and you're putting it good use...that is when I'd recommend diving into some Python and beginning to learn how it works. At the end of the day you can (and will) use both in various situations, but I'd never suggest to anyone to NOT learn how to script in MEL. Whether it be needing to clean up a co-workers code, make changes to a script, write a Maya GUI, or write a script in an older version of Maya that doesn't have Python...there are plenty of reasons you should not skip MEL.
All that being said, PyMEL combines the best of both and is my drug of choice at the moment. Learn them all so that you can make your own call on what's best. :)
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