The surface oxidation of polypropylene films which occurs during ultraviolet irradiation in air was found to result in extensive surface restructuring. This restructuring was detected by changes in surface infrared spectra, as measured by attenuated total reflection spectroscopy, and by electron microscopy. The 997 cm−1/974 cm−1 absorbance ratio of the film surfaces increased steadily during ultraviolet degradation and was interpreted as an increase in helical ordering which resulted from backbone scission during irradiation. This scission probably also results in the increase in crystallinity detected by density changes. Electron microscopy of direct surface replicas and replicas of material detached from the oxidized film surfaces showed that surface cracking resulted during photo-oxidation, and that this oxidation penetrated selectively into the polymer structure. The replicas of detached, oxidized material showed periodic structures related to the interior morphology of the films. The observed restructuring is believed to be entirely responsible for the decrease in percentage elongation at break which results from photodegradation.