A new family of 9,9-bisalkylfluorene (F)/thiophene (T)/benzothiadiazole (B) π-conjugated copolymers for organic solar cells is reported. The structure of the reported copolymers is pseudorandom: in turn each F, T, B monomer unit is alternated to the other randomly distributed two units. Voltammetric, UV–visible, and photoluminescence measurements have been carried out to assess the optical and electronic properties of the synthesized materials. The occurring of photoinduced charge transfer towards a fullerene electron acceptor was investigated by photoluminescence quenching and light-induced electron spin resonance experiments. The copolymer having alternating thiophene monomer units and randomly distributed fluorene and benzothiadiazole units exhibits the most promising characteristics; the photophysic study shows that such polymer/fullerene blend could represent a novel and cheaper material to be used as convenient donor–acceptor system for polymer solar cells.