The anodic alkoxylation of N-phenylsulfonylpyrrole (1) yielded products of nucleophilic addition on a cation radical or cation resulting from the primary electrochemical step. 2,5-Dimethoxy-1-phenylsulfonyl-3-pyrroline (3) was isolated in 46% yield and 2,5-diethoxy-1-phenylsulfonyl-3-pyrroline (5) in 38% yield. The dimethoxypyrroline derivative 3 splits off methanol when heated, giving 2-methoxy-1-phenylsulfonylpyrrole (7).