The miniseries is to premiere on the cable network next year, coinciding with the 150th anniversary of one of America's most infamous family feuds.
Costner -- whose film credits include "The Untouchables," "Field of Dreams," "Dances with Wolves," "The Bodyguard" and "Open Range" -- will play "Devil" Anse Hatfield.
The announcement was made Monday by Nancy Dubuc, History's president and general manager.
The miniseries is to be produced by Leslie Greif's production company, Thinkfactory Media, with Costner as a producing partner.
"The Hatfields and McCoys is a classic tale of American history. These are names that are widely recognized, yet few people know the real story that made them famous. We are thrilled that Kevin Costner, one of the most iconic American actors of our time, will be starring as Devil," Dubuc said in a statement. "I am confident that History will reacquaint viewers of our generation with this fascinating and timeless saga of courage, sacrifice and family love amid insidious plots and endless intrigue."
"Everyone knows the legend of the Hatfields-McCoy feud, but few know the true story of what occurred to make the two families become mortal enemies," Costner said. "As an avid history fan, I am thrilled to join with Leslie Greif and History in this dramatic re-telling of a classic and timeless tale that is forever immersed in the folklore of our country."
History made headlines this year after it ordered the $25 million, eight-part miniseries "The Kennedys," but decided not to air it amid reports of pressure from surviving members of the Kennedy political dynasty, who were said to have found depictions of patriarch Joe Kennedy and late President John F. Kennedy unflattering.
The cable network ReelzChannel then scooped up the miniseries for a reported $7 million.