Chain‐growth polycondensation of 3‐(alkylamino)benzoic acid alkyl esters 1 was investigated for obtaining poly(m‐benzamide)s with defined molecular weights and low polydispersities. Polymerization conditions were first studied to find that ethyl 3‐(octylamino)benzoate (1b) polymerized in a chain polymerization manner in the presence of lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) as a base and phenyl 4‐methylbenzoate (2b) as an initiator in THF at 0 °C. The molecular weight of the polymer was controlled by the feed ratio of monomer to initiator. The polymerization of 1c–i with a variety of N‐alkyl groups was then carried out under the established conditions to yield well‐defined poly(m‐benzamide)s, which showed higher solubility than those of the corresponding poly(p‐benzamide)s. Furthermore, the 4‐octyloxybenzyl group on the amide nitrogen in poly1i was removed by treatment with trifluoroacetic acid (TFA) to give N‐unsubstituted poly(m‐benzamide) (poly1j) with a low polydispersity, which is soluble in DMAc and DMSO, contrary to the para‐substituted counterpart. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4990–5003, 2006