Abstract: A novel tetrafluorobenzene and 4,8-di(2-(2-ethylhexyl)thiophene-5-yl)-benzo1,2-b:4,5-b’dithiophene based push-pull π-conjugated polymer, PBDT4F, was designed and synthesized via Stille coupling polymerization method, and applied for electron donor polymer in polymer solar cells. It was characterized by ¹H-NMR, gel permeation chromatography (GPC), thermogravimetric (TG) analysis, UV-Vis absorption and cyclic voltammetry (CV), etc. Results showed that PBDT4F showed good solubility in common organic solvents, such as toluene, chloroform, chlorobenzene, which was favorable for solution processed organic photovoltaic devices. The number average molecular weight (M_n) and polydispersity index (PDI) of PBDT4F were 2.36×10⁴ and 1.84, respectively. PBDT4F exhibited a strong absorption in the short wavelength of 400−600 nm, with a wide band gap of about 2.08 eV, which was complementary with that of small molecular electron acceptor O-IDTBR. PBDT4F also showed a typical low-lying highest occupied molecular orbital (HOMO) energy level of about −5.60 eV and a lowest unoccupied molecular orbital (LUMO) energy level of about −3.06 eV. The photovoltaic devices were fabricated based on the composite films of PBDT4F electron donor and O-IDTBR electron acceptor, and displayed a modest power conversion efficiency (PCE) of 2.58% with a high open-circuit voltage of 0.986 V.