The synthesis, characterization, and photophysical and photovoltaic properties of two anthracene‐containing wide‐band‐gap donor and acceptor (D–A) alternating conjugated polymers ( P1 and P2 ) are described. These two polymers absorb in the range of 300–600 nm with a band gap of about 2.12 eV. Polymer solar cells with P1 :PC71BM as the active layer demonstrate a power conversion efficiency (PCE) of 2.23% with a high Voc of 0.96 V, a Jsc of 4.4 mA cm−2, and a comparable fill factor (FF) of 0.53 under simulated solar illumination of AM 1.5 G (100 mW cm−2). In addition, P2 :PC71BM blend‐based solar cells exhibit a PCE of 1.42% with a comparable Voc of 0.89 V, a Jsc of 3.0 mA cm−2, and an FF of 0.53.