Yes you can as long as your Mac has bluetooth, I have before.
If you go to the bluetooth preferences, there is an option in there to set up a new device. Go through that, it is pretty much the same as setting up the headset with a mobile phone on the headset side. Once they are paired, just open up Skype and in the Skype preferences there is an option to choose what audio source/output to use. Just select your headset and you are good to go.
Quick note, I found that Skype can become unstable to the point of having to do a restart to get it to work properly again if you start Skype before connecting/turning on your bluetooth headset. Now this was with an older version so it may have been fixed by now.