Pressed selector

You can do this if you use an <a> tag instead of a button. I know it’s not exactly what you asked for, but it might give you some other options if you cannot find a solution to this:

Borrowing from a demo from another answer here I produced this:

a {
  display: block;
  font-size: 18px;
  border: 2px solid gray;
  border-radius: 100px;
  width: 100px;
  height: 100px;
  text-align: center;
  line-height: 100px;
}

a:active {
  font-size: 18px;
  border: 2px solid green;
  border-radius: 100px;
  width: 100px;
  height: 100px;
}

a:target {
  font-size: 18px;
  border: 2px solid red;
  border-radius: 100px;
  width: 100px;
  height: 100px;
}
<a id="btn" href="#btn">Demo</a>

Notice the use of :target; this will be the style applied when the element is targeted via the hash. Which also means your HTML will need to be this: <a id="btn" href="#btn">Demo</a> a link targeting itself. and the demo http://jsfiddle.net/rlemon/Awdq5/4/

Thanks to @BenjaminGruenbaum here is a better demo: http://jsfiddle.net/agzVt/

Also, as a footnote: this should really be done with JavaScript and applying / removing CSS classes from the element. It would be much less convoluted.

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