Feed the following CSS fragment to the validator using the CSS level 3 profile:
@namespace xlink "http://www.w3.org/1999/xlink";
a[xlink|href] { color: red; }
It will report a parse error on [xlink|href]. However, as far as I know the syntax is correct.
I also tried using a namespace on an element name instead of on an attribute name, but that also leads to a parse error.
The @namespace rule is parsed without problems, so there is some kind of namespace support in the parser.