I don't think you can do that with greasemonkey.
You can setup a handler for certain file types. When Firefox encounters one of those types, it will launch the application associated with the type. You can create a script that returns the phone number and mime type header of text/voip. Have a wrapper application open the file and pass the parameters to the voip app.
This will require your users to install your voip wrapper program. The installer for the voip wrapper should associate itself with text/voip mime types.
How to associate mime types on windows.
Thats how I'd do it.
edit
In PHP the server side code for this might look like
<?
header("Content-Type: text/voip\n");
echo $_REQUEST['phone'];
?>
You would call it like:
<a href="callPhone.php?phone=555-555-5555">Call this number!</a>
it would contain
Content-Type: text/voip (This would only be in the header, you would never see this in the file)
555-555-5555