Four novel alternating copolymers bearing 5-fluoro-6-((2-octyldodecyl)oxy)benzo[c][1,2,5]thiadiazole as a strong acceptor unit and 9,9-dioctylfluorene as a strong donor unit with bridging units namely, thienothiophene, selenophene, 3-hexylthiophene, and thiophene were designed and synthesized. The polymers were characterized via 1H NMR spectroscopy, and weight average molecular weights were reported via gel permeation chromatography (GPC). For synthesized novel polymers, the bulk heterojunction solar cells were constructed. Besides, the effects of bridging units on electronic, optical, photovoltaic, and morphological properties were investigated. Among the polymers, the thienothiophene containing polymer P1 exhibited the highest PCE as 4.25% under the illumination of AM 1.5 G with 100 mW/cm2.