Summary: For the convenient synthesis of well‐defined poly(N‐octyl‐p‐benzamide)s with low polydispersities, the polycondensation of methyl 4‐octylaminobenzoate (1) was investigated. Methyl ester monomer 1 polymerized with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) in the presence of an initiator in tetrahydrofuran at −10 °C. The highly pure polyamide with a defined molecular weight and a low polydispersity is obtained after simple treatment of the reaction mixture with aqueous NaOH solution, followed by evaporation.The chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester (1) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).magnified imageThe chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester (1) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).