The actor is known for her roles in the BBC One polive procedural as well as in This Is England, but will begin filming the new series this autumn in her home town of Nottingham.
Without Sin features McClure as Stella Tomlinson, whose 14-year-old daughter Maisy is found dead in the family home with the bloodied, hooded figure of Charles Stone standing over her.
Three years on from the death of her only child, Stella is tortured by her loss and lives a nocturnal life as an Uber driver while husband Paul is estranged and continues to live in the family home.
But when Stella and Paul are contacted by the restorative justice system and asked whether Charles can leave them a recorded message which they believe will be his apology for murdering their daughter, their lives are turned upside down once more.
Stella decides to visit the prison where Charles is held to meet him in person, bu what he actually has to say to her is so completely unexpected that it leaves her in shock.
Without Sin follows the relationship between Stella and Charles, and what really happened on the night that Maisy died.
Charles will be played by The Salisbury Poisonings and Medici actor Johnny Harris.
The four-part drama is set to film in Nottingham this autumn and McClure has called being able to work in her home city "a dream come true".
Line Of Duty fans are still eagerly awaiting news on whether McClure and co-stars Martin Compston and Adrian Dunbar will return for a seventh season of the Jed Mercurio drama.
Compston recently told the Daily Star: "People want us to come back and that's amazing. But Jed will only come back and do more if he believes there is a story to tell.
"He won’t come back just because we're getting bigger. He wouldn’t do another series just for the sake of it. He writes everything for a reason. If I'm told the series won’t come back I would be absolutely gutted."
Watch: Vicky McClure and Martin Compston to get AC-12 tattoos