The star, who appeared in three 007 films playing Charles Robinson, will guest star as a character called Tariq described by show bosses as "a mysterious interloper on the run from Spain" and Misfits actress Antonia Thomas will play his daughter, Samara.
The show's executive producers Adrian Hodges and Jessica Pope said: "We're excited to welcome an actor of Colin's reputation to The Musketeers. He will bring wonderful charisma and sense of mystery to the role.
"We've also been aware for some time of Antonia's wonderful work in films and TV series such as Sunshine On Leith and Misfits among numerous others. She brings such intelligence and vibrancy to every role she plays and we are thrilled to have her as Samara."
The show, based on the stories by Alexandre Dumas, pulled in around six million viewers for each episode in the first series and has been sold to 78 countries around the world - including France.