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 degrees 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. (c) 2006 Wiley Periodicals, Inc.