CSS Shake is a small utilty for finding unused CSS selectors in your stylesheets. It scans all your HTML and JavaScript files for CSS classes and IDs and reports rules that can't possibly match. It even handles classes and IDs added from jQuery.
$ cpanm CSS
$ wget https://github.com/mndrix/css-shake/raw/master/css-shake
$ ./css-shake my-styles.css
Unused CSS selectors:
#foo #bar ul.baz (no #bar)
li.widget (no .widget)
CSS Shake is still in very early development. It might not work for you at all.