A new azine polymer poly(4,4′-didodecyl-2,2′-bithiophene-azine) (PDDBTA) was synthesized in only three steps. PDDBTA showed hole mobilities of up to 4.1 × 10⁻² cm² V⁻¹ s⁻¹ in organic thin film transistors (OTFTs) as a p-channel material. As a donor in organic photovoltaics (OPVs), power conversion efficiencies (PCEs) of up to 2.18% were achieved, which is the first example of using an azine-based polymer for OPVs. These preliminary results demonstrate the potential of bithiophene-azine polymers as a new type of low-cost semiconductor material for OPVs and other organic electronics.