A straightforward protocol for diarylannulated sulfone construction is efficiently established via SO2/I exchange of iodonium(III) salts. Readily available inorganic Na2S2O5 was served as a safe and convenient SO2 surrogate. Diverse functionalized diarylannulated sulfones were smoothly achieved in good to excellent yields with great functional group compatibility. Organic light emitting diodes (OLEDs) material molecules were subsequently established via this method in gram scale. The unsymmetrical conjugated systems with donor-acceptor groups and π-conjugation bridges motifs, which substantially communicate electron mobility in semiconductor material molecules, were successfully afforded under the facile conditions of the exchange strategy.