For fabricating semiconductor devices and for microelectromechanical systems, photoresists are important materials supporting photolithography processes. However, photoresists must be removed for subsequent processes. An earlier study demonstrated that adding a small amount of oxygen gas to the atmosphere in which hydrogen radicals are produced increased the decomposition rate of a positive-tone novolac photoresist. For this study, we prepared polymers with different side chain structures based on poly(vinyl phenol) (PVP). We examined the effects of added oxygen and the oxygen-added hydrogen radicals on the decomposition rates of PVP-based polymers. Hydroxyl groups of PVP are partly substituted with tert-butoxycarbonyl groups in order to use for base polymer of KrF photoresist. Results show that oxygen addition can be useful for KrF photoresist removal.