Mr Travolta, who will also serve as a producer on the 10-episode miniseries, has been cast as Robert Shapiro, a key member of Simpson's 'Dream Team' during the murder trial, reports variety.com.
The other members in the cast include actors David Schwimmer, who will play Robert Kardashian, Sarah Paulson, who will portray prosecutor Marcia Clark and Cuba Gooding Junior, who will star as Simpson.
The miniseries marks Mr Travolta's first TV role since his 1979 released TV series Welcome Back, Kotter.
Executive producers of American Crime Story: The People v. O.J. Simpson are Murphy, Nina Jacobson, Brad Simpson, Alexander, Karaszewski, Brad Falchuk and Dante Di Loreto.
American Crime Story: The People v. O.J. Simpson, based on Jeffrey Toobin's book The Run of His Life: The People v. O.J. Simpson, will begin production this year.