Forty works by the godfather of pop art, including depictions of Lenin, Mao, and former US presidents Jimmy Carter and Richard Nixon, will be part of the show to be held in the Scottish Parliament.
Some of the works have never been exhibited outside of the Andy Warhol Museum in Pittsburgh, with the free-to-enter but "priceless" show opening on October 4. It has been arranged by the Carnegie UK Trust, and gifted to the Parliament by the Carnegie Museums of Pittsburgh in recognition of the UK trust's centenary.
The trust is one of 20 organisations set up by Andrew Carnegie, the Scottish-American industrialist and philanthropist born in Dunfermline, who also built Pittsburgh's Steel Company, later to become US Steel.
Warhol, from Pittsburgh, took free art classes at the Carnegie Institute, now the Carnegie Museum of Art, and then studied at the Carnegie Institute of Technology, now Carnegie Mellon University.
The steel magnate from Fife gave away the equivalent of $4.8 billion, with the Andy Warhol: Pop, Power and Politics show being the latest result of his legacy. The exhibition, which will run until November 3, will include Warhol's Flash-November 22, 1963, screen prints about the assassination of John F Kennedy as well as his portrait of Carnegie.
The theme will be power, politics and philanthropy, and will feature Warhol's Hammer and Sickle paintings, a graphite portrait of Mao Tse-Tung, Nixon and an image of Queen Elizabeth.
Eric Shiner, director of the Warhol Museum, said: "There has not been a Warhol show like this before, and we are very excited about that, a show inside a building of government like this.
"It is a perfect fit on a number of levels, and I am sure Andy would be very happy to see this happen. He was very interested in politics, in looking at politicians and people in positions of power."
Speaking from Pittsburgh, the Presiding Officer Tricia Marwick said: "It gives me great pleasure to sign this agreement which will bring over 40 of Warhol's iconic pieces to the Scottish Parliament."
The Warhol exhibition opens a programme of activities called Andrew Carnegie's International Legacy: Shaping the Future.
The climax of the festival will be the presentation of the Carnegie Medal of Philanthropy, and the winner will be announced by the Carnegie Corporation of New York.