Abstract We present the synthesis and characterization of a novel copolymer from benzodithiophene and alkylsulfanyl-bithiophene units, poly[4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene-alt-4,4′-bis(octylsulfanyl)-2,2′-bithiophene] (PolyS). The structural, electrochemical and photophysical properties of PolyS were investigated by gel permeation chromatography (GPC), thermogravimetric analysis (TGA), NMR, UV–vis, photoluminescence (PL) spectroscopy and cyclic voltammetry (CV). PolyS was used to fabricate bulk-heterojunction polymer solar cells (PSCs) in combination with the [60]PCBM and [70]PCBM (electron acceptors). The device realized using [70]PCBM shows a better current output due to the increased absorption of the blend film compared to the PolyS:[60]PCBM one. The power conversion efficiency of the best PSC realized is 2.3% under 100 mW/cm2 AM 1.5 G illumination.