A simple and efficient approach for the preparation of rod-coil block copolymers comprising oligo- and polythiophenes blocks together with PMMA or PS blocks is described. The block copolymers were prepared using a two-step procedure. α,ω-dicarboxy-terminated oligothiophenes and carboxy terminated poly(3-hexylthiophene) were first prepared. These were then reacted with P4S10 in a second step to generate the α,ω-thioester terminated oligothiophenes and poly(3-hexylthiophene)s which were subsequently used in a one-pot reaction as RAFT polymerization agents with methylmethacrylate and styrene. The di- and tri-block copolymers hence obtained were fully characterized, both in solution and as thin films.