Recently, the benzodithiophene- (BDT-) based polymers with conjugated side groups attracted considerable attention due to their superior properties in polymer solar cells (PSCs), so the investigation of the side chain effects on the photovoltaic properties of this type of polymers is an interesting and important topic for molecular design. Herein, three conjugated polymers based on BDT and thieno[3,4-b]thiophene units with furan, thiophene and selenophene as side groups, named as PBDTTT-EFF, PBDTTT-EFT, and PBDTTT-EFS, were synthesized and applied in polymer solar cells. The polymers were characterized in parallel by absorption spectroscopy, thermogravimetric analysis (TGA), density functional theory (DFT), ultraviolet photoemission spectroscopy (UPS), X-ray diffraction (XRD), and photovoltaic measurements. The results show that the dihedral angles between the BDT and conjugated side groups play important roles in affecting the absorption bands, HOMO levels, crystallinities, and aggregation sizes of the polymers. The photovoltaic results indicate that PBDTTT-EFT and PBDTTT-EFS show similar photovoltaic characteristics in device, and PCEs of 9.0% and 8.78% were obtained, respectively. The device of PBDTTT-EFF shows a V-oc of 0.69 V and a J(sc) of 11.77 mA/cm(2), which are lower than those in the devices based on the other two polymers. Overall, this work suggests that the photovoltaic properties of the BDT-based polymers can be effectively tuned by introducing conjugated side groups with varied steric hindrance.