Surface modification of polymers by low-pressure plasmas has gained scientific and industrial importance for controlling adhesion of coatings, wettability, printability, bio-compatibility and other surface-related properties. However, more is to be learned about the complex interactions at the plasma-polymer interface. The present study is designed to investigate these plasma-polymer surface interactions by means of mass spectrometry. Various polymer specimens (polyethylene, polypropylene, polyethylene terephthalate, and polyimide) were placed directly on an electrode which contains the sampling aperture into a quadrupole mass spectrometer. We have identified various molecular fragments from these polymers, which were liberated by chain scissions provoked by various energetic plasma constituents, in particular, bombarding ions and vacuum ultraviolet (VUV) photons.