The spreading characteristics of thin polymeric liquid films of perfluoropolyalkylethers (PFPEs) Fomblin Z15 and Fomblin Zdol (hydroxyl terminated PFPE) on silica surfaces have been measured by scanning microellipsometry (SME). We estimated the surface diffusion coefficients and propose a modified diffusion equation to interpret the spreading phenomenon from film thickness profiles measured with SME. We investigated the spreading of Z15 as a function of binary blend ratio of monodisperse Z15 fractions and found that the surface diffusion coefficients of the blends do not obey a simple linear mixing rule. A summary of thin PFPE film spreading characteristics as a function of molecular weight, film thickness, chain-end functionality, temperature, and humidity is presented.