This has driven me nuts ever since I started using Rdio (sign up using this link to support me). I like to listen to other peoples playlists to find new music and if I hear something I like I add the track to my "favorites" playlist. Unfortunately Rdio lets you add the same song multiple times to the same playlist and there isn't an easy way to find and remove duplicates so I end up with Ice Cube's Check Yo Self in my favorites 5 times.
Here's my solution.
1) Install this bookmarklet by dragging it to your bookmarks or right clicking and selecting "add to bookmarks"
2) Browse to the playlist you want to cleanup in Rdio
3) Run the bookmarklet.
If you're interested in other Rdio hacks be sure to checkout my Rdio remote control PartyQ