Three linear SMs of (DRCN3T)2Ar with arylene (Ar) and dicyanomethylene-rhodanine units were synthesized. The influence of the Ar unit on optoelectronic properties of (DRCN3T)2Ar was studied. The anthrylene-based (DRCN3T)2Ant exhibited best photovoltaic properties in OSCs with a promising PCE of 5.15%.