Under the agreement, the Richard Desmond-owned broadcaster will have exclusive terrestrial rights to the third season of hit drama The Mentalist.
In the autumn/winter schedule, Five USA will air Jerry Bruckheimer Television's undercover police drama Dark Blue, which stars Golden Globe winner Dylan McDermott.
The digital channel will also broadcast Blade: The Series, which is based on the comic books and film trilogy about an immortal warrior who battles vampires.
Sister channel Fiver will broadcast action drama Human Target, which stars Fringe actor Mark Valley as a mysterious security agent for hire.
Channel Five's managing director of digital channels and acquisitions Jeff Ford said: "I am thrilled to have secured this wide-ranging deal for Channel Five. I am delighted to welcome back the critical and ratings smash The Mentalist for another season.
"The addition of Dark Blue and Human Target strengthens our burgeoning slate of quality offerings on the digital channels. Plus, the movie lineup is an exciting mix of terrestrial premieres and blockbuster films for all the family."
Warner Bros. International Television president Jeffrey R. Schlesinger added: "We are always looking to place our programming on the right networks where they can thrive and connect with viewers.
"You don't have to be a mind reader to know the best continuing home for The Mentalist is Channel Five, where they have contributed to this show becoming one of the most popular US series being telecast in the UK today.
"The commercial appeal of shows like Dark Blue, Human Target, Blade and these selected top feature films also make this programming perfectly suited to be telecast and succeed on Five's family of channels."
Five has also secured a raft of film rights, including terrestrial premieres of 300, Beowulf, 10,000 BC and Teenage Mutant Ninja Turtles.
The broadcaster will also air a range of archive titles, such as The Matrix trilogy, The Last Samurai and The Perfect Storm.