Developing photovoltaic materials with simple chemical structures and easy synthesis still remains a major challenge in the industrialization process of organic solar cells (OSCs). Herein, an ester substituted poly(thiophene vinylene) derivative, PTVT-T, was designed and synthesized in very few steps by adopting commercially available raw materials. The ester groups on the thiophene units enable PTVT-T to have a planar and stable conformation. Moreover, PTVT-T presents a wide absorption band and strong aggregation effect in solution, which are the key characteristics needed to realize high performance in non-fullerene-acceptor (NFA)-based OSCs. We then prepared OSCs by blending PTVT-T with three representative fullerene- and NF-based acceptors, PC