π-Conjugated block copolymers have been prepared from terminal azide functionalized polystyrenes (PS) and alkyne functionalized poly(3-hexylthiophene)s (P3HT) via a copper(I) catalyzed Huisgen [3 + 2] dipolar cycloaddition reaction. The functionalized α-azido-PS homopolymer was prepared by atom transfer radical polymerization from a specifically designed initiator bearing the azide function, whereas ω-ethynyl-P3HT and α,ω-pentynyl-P3HT were synthesized by a modified Grignard metathesis polymerization using alkynyl Grignard derivatives. The electronic environment of the alkynyl end groups was shown to be decisive in determining triazole ring formation.