Binary mixtures of 4'-octyl-4-biphenylcarbonitrile (8CB) and n-tetracontane (C40H82) deposited-as crystalline monolayers from a bulk fluid droplet on a graphite substrate were found to undergo nanometer-scale phase segregation into pure 8CB and pure alkane domains. Film morphology, molecular ordering, and domain motion were studied using scanning tunneling microscopy. Alkane adsorption was favored in the early stages of film growth, which was followed by a period of gradual annealing in which 8CB displaced alkane molecules from the surface. The structure and composition of the monolayer show that in films deposited from a bulk fluid with a 600:1 molar ratio of 8CB/-tetracontane 8CB adsorption is thermodynamically favored. However, n-tetracontane had a significantly larger nucleation rate, leading to high alkane surface coverage shortly after film formation. Quantitative rate measurements of alkane domain replacement by 8CB have been made and correlated with the microscopic structure of the 8CB-alkane interface.