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I'm assuming you want to learn how to use RGSS, correct? Well, there are plenty of tutorials around the forums(I think.), and you can also check out the scripting academy.
The Pragmatic Programmer's Guide to Ruby is a great reference. RPG Advocate has made an excellent index of default scripts and even explains what they do. There's a bit of syntax here too, along with several scripts.
There's also the helpfile, although it's not very helpful (hehe)
Finally, just looking through the default scripts and changing a few things to see what happens is a good way to gain an understanding of how the scripts work.