Poly(3‐heptylselenophene)‐stat‐poly(3‐hexylthiophene) is synthesized and characterized in terms of its crystallinity and performance in an organic photovoltaic (OPV) cell. Despite the random distribution of units along the polymer main chain, the material is semi‐crystalline, as demonstrated by differential scanning calorimetry and wide‐angle X‐ray diffraction. Thin‐film absorption suggests an increased compatibility than seen with 3‐hexylselenophene monomer. Optoelectronic properties are an average of the two homopolymers, and OPV performance is enhanced by a broadened absorption profile and a favorable morphology. Poly(3‐heptylselenophene)‐stat‐poly(3‐hexylthiophene) is synthesized, characterized, and fabricated into photovoltaic devices. The copolymers are crystalline despite the random distribution of units along the backbone. Optoelectronic properties of the copolymer are an approximate average of the corresponding homopolymers, while the morphological properties are distinct.