In recent years, all-polymer solar cells (all-PSCs), incorporating active layers based on blends of electron-donor (D) and acceptor (A) polymers, have drawn attention because of the advantages they hold in the flexibility of choosing the D:A combinations to modulate their energy levels and to improve their overall open-circuit voltages (V-oc)) and power conversion efficiencies (PCE)s. V-oc is one of the key parameters for the determination of the PCEs of PSCs. In this work, we synthesized six donor polymers with three different side chains appended to the 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (BDT) units. By substituting carbon with sulfur and silicon atoms at the 5-position of the thiophenes attached to the BDT units, the highest occupied molecular orbital (HOMO) levels of the donor polymers could be successfully lowered. As anticipated, the V-oc values of the resulting all-PSCs increased along with the lowering of the HOMO levels of the donor polymers. Among the six allPSCs, the PBDT-BDD:PNDI-T10 all-PSC realized a balance between the photovoltage and photocurrent, where a decent PCE of 5.6% was obtained with a V-oc of 0.9 V-oc and a photocurrent of 10.5 mA/cm(2).