The efficient synthesis of regioregular poly(3-hexylthiophene-2,5-diyl)s (rr-P3HTs) capped with chalcogens using a simple quenching method is reported. Thiol (SH) end groups are selectively installed at the terminating end (ω-end) or at both the initiating (α-) and ω-ends using sulphur powder or triisopropylsilanethiol (TIPS-SH), respectively.