A simple but efficient route to the preparation of aromatic end-functionalized regioregular poly(3-hexyl thiophene) through catalytic initiated Kumada catalyst transfer polymerization from easily accessible reagents is reported here. The introduction of an aromatic moiety at one end of the poly(3-hexyl-thiophene) (P3HT) chain was confirmed by NMR, by MALDI-TOF analysis, and also by successful syntheis of rod-coil-conjugated block copolymers either from a proper end-functionalized P3HT or from an end-functionalized coil polymer.