Degradation behaviors of both the unplasticized and plasticized poly(vinyl chloride) (UPVC and PPVC) under an artificial accelerating aging condition were extensively studied. The dependence of mechanical properties, average molecular weight (MW), and surface morphology of the earlier PVC on aging time was investigated by tensile tests, gel penetrate chromatogram (GPC), and scanning electron microscope (SEM), respectively. Fourier transform infrared and ultraviolet (UV)visible spectroscopy were used to evaluate the probable formation of both the oxygen-containing groups and the conjugated sequences during aging. The results reveal that UPVC is much easier to be degraded than PPVC under the same testing conditions. The irradiated surface is detected to change from an even topology into a rough topology initially, and then follows the appearance of many voids even cracks in the SEM morphology. During the aging process, oxygen-containing groups and conjugation of PVC molecular chains around the cracks are observed, and noticeably increase with aging time. However, visible difference of the corresponding MWs of PVC before and after aging is not detected. Moreover, a novel degradation mechanism nearly related to the formation of microvoids and microcracks based on the cohesion energy of groups along PVC molecular chains is developed and semiquantitatively discussed. It is detected that the formation of microvoids and microcracks is attributed to both the thermodynamic changes of PVC backbone during the aging and the aggregation of oxygen-containing groups with relatively large volumes. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012