Plasma‐induced polystyrene radicals were first studied by electron spin resonance (ESR). The room temperature ESR spectrum was compared with those obtained by γ‐irradiation, UV‐irradiation, and mechanical fracture. It was found that even less than a few seconds of plasma‐irradiation gave rise to a large amount of polystyrene radicals and the ESR spectrum consisted of two types of spectra, a triplet and a single broad line. The spectral feature of the triplet was nearly identical with that of γ‐irradiated polystyrene. Thus, it was assigned to the structure of a cyclohexadienyl‐type radical formed by a nearly random addition of a hydrogen atom to the aromatic ring. The single broad line, thought to be an outline of multicomponent spectrum, was assigned to an immobilized dangling‐bond sites at the plasma‐induced crosslinked portion of the polystyrene surface.