Semiconducting polymers have been developed during the last few decades and are currently used in various organic electronics applications. Regioregular poly(3-hexylthiophene) (P3HT) is the most employed semiconducting polymer for organic electronics applications. The development of living Grignard metathesis polymerization (GRIM) allowed the synthesis of P3HT with well-defined molecular weights and functional end groups. A large number of block copolymers containing P3HT have been reported, and their opto-electronic properties have been investigated. The performance of P3HT homopolymer and block copolymers in field-effect transistors and bulk heterojunction solar cells are discussed in this review. The morphology of the P3HT materials is also discussed.