The 29-year-old was released by Brentford at the end of the season, and has signed a two-year deal at Millmoor.
Millers boss MickHarford said: "I am sure Deon will be a major asset to this club. He is a good target man who can also hold the ball up well and I am absolutely sure he will do a good job for us.
"He once commanded a fee of £1million, has played at the highest level in the Premiership and I am really looking forward to working with him here."