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CSS2.1 is stable, old, compatible (IE8+).
CSS3 is new, cool, sometimes buggy, vendor-prefixed, and not cross-browser [yet].
But to be more specific, CSS 3 is not a monolith spec anymore. It consists of modules which have different writing and adoption speeds. Some of them are everywhere now, some are far from it. Look at W3C site for specific modules, and at vendor sites for what parts of CSS3 they currently support.
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