Aging phenomena of plasma polymer films were studied by using the surface analysis techniques of contact angle measurement, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOFSIMS), and atomic force microscopy (AFM). The polymer films were grown on an aluminum substrate by using a plasma polymerization method from a gas mixture of acetylene and helium, and the films were subsequently modified to have a hydrophilic surface by oxygen plasma treatment. Aging of the polymer films was examined by exposing the samples to water and air environments. The aging process increased the hydrophobicity of the surface, as revealed by an increase in the advancing contact angle of water. XPS analysis showed that the population of oxygen-containing polar groups increased due to the uptake of oxygen during the aging, whereas TOF-SIMS analysis revealed a decrease in the polar group population in the uppermost surface layer. The results suggest that the change in surface property from hydrophilic to hydrophobic nature results from the restructuring of polymer chains near the surface, rather than compositional change of the surface. Oxidative degradation may enhance the mobility and the restructuring process of polymer chains.