Herein, two new 5,6-alt-benzothiadiazole-based Poly(o-arylene-vinylene) (POAV) type of D-pi-A-conjugated copolymers, namely P1 and P2, have been synthesized using Horner-Wittig reaction and characterized by UV-Vis, H-1 NMR, C-13 NMR, and CV. With a deeper HOMO level of ae 5.95 eV, these two polymers have been used as donor with [6, 6]-phenyl C61-butyric acid methyl ester, PC61BM as an acceptor to fabricate solar cells with a device structure ITO/PEDOT:PSS/P1orP2-PCBM/Al or Ca:Al. Without annealing or use of additives, maximum V (oc) of 0.68, fill factor of 30.2%, quantum efficiency of 22%, and maximum power conversion efficiency (PCE) of 0.76% have been achieved with P2. Morphology of blended active layer, P1/P2 with PC61BM and PC71BM, has been investigated using AFM images. [GRAPHICS] .