Polymer-bound photoacid generators (PAGs) (anion bound) and their corresponding polymers were synthesized for evaluation of the reactivity of polymer-bound PAGs with secondary electrons in solutions by the electron beam pulse radiolysis method. In the solutions, the rate constants of polymer-bound PAGs are much lower than those of polymer-blend PAGs. In addition, we evaluated the acid generation efficiencies of polymer-bound PAGs. As a result, despite the film state, the acid generation efficiency of polymer-bound PAGs are about 10% lower than those of the polymer-blend PAGs. These differences are explained by the difference in stabilization effects between polymer-bound PAGs and polymer-blend PAGs in both solutions and films.