Of course you can. You can commute on any functioning bike. But if you make bike commuting a commitment and a regular part of a long term routine I think you'll discover a carbon fiber race bike has many shortcomings as a commuter.

For the price of one Madone you could buy a nice dedicated commuter AND a nice road bike.

edit- With that said: Ride what you like. if a Madone works for you then by all means ride the wheels off the thing.