We report a photoredox system comprising sodium iodide, triphenyl phosphine, and N,N,N',N'-tetramethylethylenediamine (TMEDA) that can form a self-assembled tetrameric electron donor-acceptor (EDA) complex with diaryliodonium reagents (DAIRs) and furnish aryl radicals upon visible light irradiation. This practical mode of activation of DAIRs enables arylation of an array of heterocycles under mild conditions to provide the respective heteroaryl-(hetero)aryl assembly in moderate to excellent yields. Detailed mechanistic investigations comprising photophysical and DFT studies provided insight into the reaction mechanism.