The Graham Yost-created series, which is based on the novels by Elmore Leonard, premiered Tuesday night on FX in the States.
The show, which also stars Nick Searcy, Erica Tazel and Jacob Pitts, centres on Deputy US Marshal Raylan Givens (Olyphant) and is set in Kentucky.
Five's Jeff Ford commented: "I'm delighted to announce this fantastic addition to the Five USA schedule. Olyphant is an excellent lead and has the same, compelling presence as Clint Eastwood in the classic Coogan's Bluff.
"This exclusive acquisition bolsters the strong schedule and reaffirms that Five USA is the place to come for quality American drama on British TV."
The deal will see the 13-episode first season of Justified play out on Five USA from April.