Poly(3-alkylthiophenes) (PATs) exhibit promising electronic properties; however, their regioregular syntheses are only beginning to be developed. The authors describe a new method for the preparation of head-to-tail coupled (HT) PATs, in which methylmagnesium bromide is utilized to effect a Grignard metathesis that displays unexpectedly high regioselectivity. The method produces regioregular HT-PATs quickly, economically and in high yields, which lends it excellent potential for industry-level production.