The electroreduction of polyacrylamide derivatives in DMF using tetraalkylammonium salts (R4NX) as supporting electrolytes has been found to yield the corresponding anionic species possessing interesting reactivities as electrogenerated bases (EGBs). The homopolymer of n-methylacrylamide (MAAm) and its copolymers with N,N-dimethylacrylamide (DMAAm) and styrene (St) were used as polymeric probases and the reactivity of the resulting polymer EGBs was investigated. The polymer EGB prepared from the copolymer of MAAm with DMAAm [copoly(MAAm-DMAAm)] containing 65% of MAAm unit gave the best result in the trichloromethylation of alpha,beta-unsaturated esters (89%). It was also found that polymeric probases were easily recovered by reprecipitation and they were repeatedly useable as probases.