Poly(tetrafluoroethylene)(PTFE) films were surface modified in a solution of benzophenone and sodium hydride in dry dimethylformamide by ultraviolet (UV) light irradiation. The extent of surface modification was characterized after durations of UV light irradiation from 5-20 min at temperatures from 19-60 degrees C. The modified films were analyzed by electron spectroscopy for chemical analysis, diffuse reflectance ultraviolet-visible light spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, dynamic contact angle measurement, and low-voltage scanning electron microscopy. PTFE surfaces produced by this modification demonstrated extensive defluorination, oxygen incorporation, surface unsaturation, and reduction in both advancing and receding dynamic water contact angles in a manner that was more extensive at long durations of irradiation and at high temperatures. Morphological damage depended upon treatment conditions, but extensive surface modification could be obtained without substantial morphological damage to PTFE films. Control experiments indicated that the surface modification proceeded by photoexcitation of either diphenyl ketyl radical anion or benzhydrol anion, the products of reaction of benzophenone with sodium hydride.