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The film received mixed, though mostly positive, reviews gaining 61% on Rotten Tomatoes based on 142 reviews, with the consensus that "Keira Knightley squeezes into a corset again, and pulls off another worthy performance in this sumptuous and emotional period drama, that serves parallels to the Duchess's descendent Princess Diana." Peter Bradshaw of The Guardian wrote that "Dibb's movie looks good" [however] "exasperatingly bland and slow-moving at all times" handing out a 2 of 5 star rating. However, Paul Hurley gave the film 8/10 and called The Duchess "an excellent new film" and states that "The Duchess stands a good chance of taking home some very big prizes at the end of the year".

Most reviewers have highly praised Knightley and Fiennes' performances. Timeout London wrote: "[Saul Dibb] is also helped enormously by a mature, restrained portrayal from Knightley, a masterclass in passive aggression from Fiennes and a performance of tender seduction from Atwell." The Epoch Times writes, "Ralph Fiennes brings a human quality to [the Duke] by avoiding any intent, exaggeration or ill will" and "Keira Knightley’s performance gains new depth — she not only perfectly portrays a witty and feminine Georgiana early in the film, but also a caring mother, and an abandoned woman later on. Also remarkable in this role is Knightley’s ability to portray the strengths, weaknesses, and the internal hurdles of Georgiana, as well as her internal contemplation." Film Ireland writes "It is a slow movie but it is well acted with Knightley and Fiennes suited to their roles, especially Fiennes who gives a formidable and powerful performance."

Cameron Baily, the co-chair of The Toronto International Festival comments; “The Duchess Of Devonshire, with Keira Knightley, which is a beautiful film and she gives a really mature performance. You’re seeing her really turn into something beyond the kind of pretty face that we’ve seen her do already so well. But she’s actually a very serious actress and she’s turning into a great, great performer.”

It won the 2008 Academy Award for Costume Design.