As the new face of the heir, West takes over from Josh O'Connor, who was widely praised for his portrayal of a prince torn between love and duty in seasons three and four.
Covering the destruction of his marriage to Princess Diana (who will be played by Elizabeth Debicki) and his continuing love for Camilla Parker-Bowles, there's a lot of ground to cover.
But what will West bring to the table as he captures some of the now King's most troubled years?
Here's everything you need to know about West, where you know him from, and what he's said about his new, regal role.
Who is Dominic West, The Crown's new Prince Charles?
Born 15 October, 1969, West (born Dominic Gerard Francis Eagleton West) was the sixth of seven children. His mother Pauline was an actor, and his father Thomas was a factory owner. Both sides of the family came from Irish heritage.
West is one of the many established alumni of the prestigious Eton College. He later continued his studies at Trinity College in Dublin, earning a degree in English Literature.
From this, he decided to pursue a career in acting, and graduated from the Guildhall School of Music and Drama in 1995.
Initially working largely in television, West had a string of small roles in notable productions. For example, he played a paparazzi photographer in the 1997 Spice World: The Movie, a palace guard in 1999's Star Wars: Episode I - The Phantom Menace, the ill-fated Fred Casely in the opening scenes of the 2002 movie adaptation of Chicago, and Ebeneezer Scrooge's kind-hearted nephew Fred in a TV adaptation of A Christmas Carol.
However, arguably his breakthrough role came in the shape of Jimmy McNulty in The Wire in 2002. Since then, he's become one of the UK's busiest stars both in the UK and Stateside.
Read more: Who is Elizabeth Debicki?
In June 2010, he married university sweetheart, Catherine FitzGerald, and together they have four children – Dora, 16, Senan, 14, Francis, 13, and Christabel, 9.
He also has another daughter, Martha, 24, from a previous relationship.
What has Dominic West been in before The Crown?
The role of Officer Jimmy McNulty in The Wire undoubtedly remains one of West's most praised and known roles. Remaining in the gritty drama from 2002-2008, the star played an obsessed and self-destructive cop.
In 2011, he earned his first Bafta for his portrayal of serial killer Fred West in TV mini-series, Appropriate Adult.
West took the lead role of Noah Solloway in The Affair in 2014, joining Ruth Wilson as Alison Bailey in the drama as a couple who both deal with the long-term effects of their decision to have extra-marital affairs after a chance encounter in Montauk, New York.
The series ran for five seasons, ending in 2019, with West being the sole character to remain throughout the show's entire run.
Film credits include 2014's Pride (which his The Crown co-star Imelda Staunton also appeared in), 2018's Colette with Keira Knightley, and 2018's Tomb Raider as Richard Croft.
Most recently, he was seen opposite Lily James in The Pursuit Of Love, and Dr Chris Cox in Sky series Brassic.
At the same time The Crown airs, he'll also be seen on BBC's new war drama, SAS Rogue Heroes as Lieutenant Colonel Wrangel Clarke.
What has Dominic West said about being in The Crown?
West has actually confirmed he initially turned down the role of Prince Charles in The Crown when offered it, telling producers "you've got the wrong guy".
"I'd been watching the show, I'd been a fan from the start," West told Entertainment Weekly. "I was very conscious of Josh [O'Connor]'s amazing performance, and his amazing success, and thought it was a bit of a hiding to nothing to try to follow that."
However, he changed his mind when he "couldn't get the idea out of his head".
"[I] realised that you've got to give it a go because you'll regret it if you don't," he said. "He's a fascinating man, Charles, and it's a fascinating life, and a fascinating role."
He's also defended the series amid arguments for a disclaimer coming at the beginning of each episode, explaining The Crown is a dramatic retelling rather than real-life recreation.
"I think people understand, because the cast has changed every two seasons, that this is not an imitation," he told Netflix's TUDUM. "This is an evoking of a character. That's really where the show lives: in the imagined conversations of their private life, which is something that no one knows."
"I think that's what it gets a lot of criticism for. How can you know what they talk about in their private lives
"The obvious answer is we don't, but we have an incredible writer, a dramatist, who imagines based on exhaustive research, and that's really part of the fascination of the show."
The Crown season five airs 9 November on Netflix.
WATCH: The Crown Season 5 trailer