A new regioregular head-to-tail (HT)-type polypyridine with methoxyethoxyethoxy (MEEO) side chains, HT-PMEEOPy, was synthesized by means of Kumada-Tamao coupling polymerization of a Grignard monomer with a Ni catalyst. Although the polymer was precipitated in THF during polymerization, multiangle laser light scattering (MALLS) analysis indicated that the weight-average molecular weight (Mw) was about 25,000. The HT content in the polymer was 95%. A solution of HT-PMEEOPy in CHCl3 was found to emit a strong blue light when the solution was irradiated with UV light; the UV-vis absorption maximum (?max) and photoluminescence maximum (?max em) were at 392 and 460 nm, respectively. To clarify the effect of regioregularity of PMEEOPy on the photoluminescence, head-to-head (HH) PMEEOPy was synthesized by means of Yamamoto coupling polymerization. The photoluminescence of HH-PMEEOPy (?max = 330 nm, ?max em = 414 nm) was weaker than that of HT-PMEEOPy. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012