© 2021 Elsevier LtdTwo new random donor-acceptor (D-A) copolymers, signed as P1 and P2, were designed and synthesized. Electrochemical and spectroelectrochemical measurements were performed to investigate absorption, energy levels, electronic and optical band gaps for comparison. The polymers were used as donor polymers in the active layer to fabricate non-fullerene, bulk heterojunction (BHJ) organic photovoltaics (OPVs). Investigations were carried out through the conventional BHJ structure; ITO/PEDOT: PSS/Active Layer/LiF/Al, where active layer consists of 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC) as the acceptor and thienopyrroledione containing donors. The device based on P1:ITIC(1:1) blend with a thickness of 161 nm gave the best performance with a power conversion efficiency (PCE) of 7.94%, an open-circuit voltage (VOC) of 0.86 V, a short-current density (JSC) of 18.45 mA cm−2 and a fill factor (FF) of 50.12%. The highest PCE obtained from P2 based organic solar cell is 1.96%. P2 exhibited low solubility attributed to the lack of alkyl groups enhancing polymer solubility, electronic properties, and photovoltaic performances. The research outputs exhibit that introduction of alkyl chains on the polymer backbone can enhance device performance.