The analytical technique of contact angle analysis has been used both to monitor organic transformations on the surfaces of fluoropolymer films and also to help correlate surface structure with wettability. This paper describes the preparation and characterization, particularly with regard to wettability, of several series of surface-modified derivatives of chemically resistant polymers. A series of esters prepared with acid chlorides and alcohol-functionalized poly(chlorotrifluoroethylene) (PCTFE-OH) displays expected water contact angle trends and indicates that wettability can be controlled using organic surface chemistry. The identification of carboxylic acids on the surface of poly(vinylidene fluoride) (PVF2-CO2H) by the pH dependence of the water contact angle is discussed. Also described and compared with X-ray photoelectron spectroscopy is the use of contact angle for observing polymer surface reconstruction.