Cascade radical cyclization of N-arylacrylamides is an attractive method to prepare 3,3-disubstituted oxindoles. As the reported methods often require additives and/or photocatalysts, we herein report an additive- and photocatalyst-free deaminative strategy for their synthesis under mild conditions, enabled by photoactivation of an electron donor-acceptor (EDA) complex. DFT studies indicated that the involvement of an explicit xylene solvent molecule can greatly enhance the photoactivity of the EDA complex between N-arylacrylamides and Katritzky salts.