The alkaline hydrolysis of methyl 5-X-picolinates, methyl 4-X-picolinates, and methyl 5-X-nicotinates (X = NO2, Br, H, MeO, or Me2N) in methanol–water (85% w/w) is reported. In each series, the effect of the substituent and ring nitrogen are additive and the rates may be correlated with Hammett σm and σp values.