Two benzodifuran (BDF) polymers, PBDF-C and PBDF-S, with alkyl and alkylthio substituted thiophene side-chains and benzodithiophene-4,8-dione (BDD) as the acceptor were designed and synthesized. Their optical, electrochemical properties and photovoltaic performances were systematically investigated. The polymer solar cells (PSCs) with a device structure of ITO/PEDOT:PSS/polymer:PC71BM/Ca/Al were fabricated. The PBDF-C based device showed a power conversion efficiency (PCE) of 3.01% after adding 1 vol% 1,8-diodooctane (DIO) as the solvent additive, and PBDF-S gave an enhanced PCE of 3.48% without any post-treatments. The enhancements were from the higher open-circuit voltage (Voc) and fill factor (FF). The thermal- and solvent-treatment-free processing is more favourable for the large area roll-to-roll manufacturing or printing technology for PSCs.