Little is known about George F. Payne as a child and a young man. It is known that he was a member of the Washington Grays, serving with that Philadelphia artillery corps during the infamous railroad strike at Pittsburgh in 1877. How this experience affected Payne's attitude toward organized labor is unknown.

After his departure from the Washington Grays, he apprenticed with a carpenter and, when he had finished, went into business for himself. Payne and Charles G. Wetter together founded the Philadelphia construction firm of George F. Payne and Company in 1881.

A listing of the Philadelphia buildings that were erected by Payne and Company is quite impressive: the Bullitt building at 133–137 South Fourth Street, the Crozer building at 1420 Chestnut Street, the United Gas Improvement Company building at Broad and Arch Streets, a professional building at 1831–1833 Chestnut Street, the Perry Building at 16th and Chestnut Streets, the Loraine Hotel at Broad Street and Fairmount Avenue, the Academy of Natural Sciences at 19th and Race Streets, Widener Memorial Home on York Road above Logan, the Wistar Institute at 36th and Spruce Streets, and St. Joseph's Academy in Chestnut Hill.

Other buildings of note outside Philadelphia include the Carnegie Library; a dormitory and an agricultural building in State College; residences for Peter A. B. Widener and William L. Elkins in Ashbourne, Pennsylvania; and three Newport, Rhode Island residences.

Payne was the successful bidder for the Capitol contract over five other contractors. His firm also became a subcontractor to John H. Sanderson, the Capitol special furnishings contractor, as the Capitol project progressed.

Payne and Company was implicated in the Capitol graft scandal, and Payne, himself, was subsequently indicted for conspiracy to defraud the Commonwealth. Payne retreated to Mount Clemens, Michigan in 1907, during the investigation by the Capitol Investigation Commission. His health gradually failed and he died there during the latter part of 1907. His estate was not listed among the parties paying restitution to the Commonwealth for the Capitol graft.