His family said in a statement that he "died peacefully on Monday October 16 in his London home surrounded by family, including his three daughters, grandchildren and great-grandson".
The actor, who played Hallyne the Pyromancer in the hit TV series, also narrated George RR Martin's A Song Of Ice And Fire audiobook collection.
His narration saw him awarded a place in the Guinness World Records in 2004 for the greatest number of characters voiced in an audio book at 224.
Roy was also known for his role as Leopold Mozart in Oscar-winning film Amadeus.
Dotrice won a handful of prestigious accolades, including a Tony Award for his role in the Broadway revival of A Moon For The Misbegotten in 2000.
In 1969, he claimed the TV Bafta best actor award for his role as Albert Haddock in the BBC adaptation of AP Herbert's Misleading Cases.
He also appeared in TV series Shaka Zulu, Mr And Mrs Smith and Life Begins, and films including Eliminators, The Cutting Edge and Hellboy II: The Golden Army.
Prior to his acting career, Dotrice was in the military, which he said inspired him to become an actor.
Born on Guernsey, Dotrice joined the Royal Air Force and was trained as a wireless operator and air gunner.
His plane was shot down and he was held as a prisoner of war - where his first taste for the theatre took root, performing concerts to raise the spirits of his fellow inmates.
In 2008 Dotrice was awarded an OBE for services to drama by the Queen.
At the time, he said he had never imagined he would be receiving an honour at Buckingham Palace.
Dotrice was married to his wife Kay for 60 years, until her death in 2007.
They had three daughters together - Yvette, Karen and Michele, who is known for her role as Betty in Some Mothers Do 'Ave 'Em and who was married to actor Edward Woodward, who died in 2009.