It's using extended slicing - a string is a sequence in Python, and shares some methods with other sequences (namely lists and tuples). There are three parts to slicing - start, stop and step. All of them have default values - start defaults to 0, stop defaults to len(sequence), and step defaults to 1. By specifying [::-1] you're saying "all the elements in sequence a, starting from the beginning, to the end going backward one at a time.
This feature was introduced in Python 2.3.5, and you can read more in the What's New docs.