The only document that can be reasonably described as "definitive" is the source code of parse.y in the YARV source tree.
The ISO Draft Specification contains a 39 page appendix with a summary of the grammar. Note, however, that ISO Ruby is a minimal subset of the intersection of Ruby 1.8 and 1.9. IOW: it doesn't describe anything that is only in 1.8 or only in 1.9 (so, the syntax additions in 1.9 like stabby proc and symbol hashes aren't described), nor does it describe everything in that intersection. ISO Ruby is a bit like ISO HTML in that regard.
The RubySpec project contains executable specifications for the Ruby language. It doesn't contain an explicit specification of the grammar, though. The only specification of the grammar is implicit in the examples themselves. Also, because RubySpec is an example-based spec, it can only show you specific examples of valid Ruby code, but it cannot tell you all possible valid Ruby programs like a grammar spec could. And, because RubySpec is itself executable Ruby code, it can only show you valid examples, not invalid ones.
The last thing that could be considered definitive is the book The Ruby Programming Language by David Flanagan and Yukihiro "matz" Matsumoto.
Note, however, that "the whole of Ruby syntax" is a rather daunting task, because Ruby's syntax is insanely complicated with a ginormous amount of weird corner cases.