In this study, we successfully designed and synthesized a novel class of ladder-type polymer polydi-benzoyl[b,f][1,5]diazocine (PBDA-a) and polydimethoxybenzoyl[b,f][1,5]diazocines (PBDA-b) for novel electrochemical actuators via one-pot polymerization. The structure of polymers was characterized using C-13 NMR, FTIR and MALDI-TOF. Both of the polydiazocines exhibited high thermal stability and excellent solubility in common solvent. Molecular conformation studies using the density functional theory method revealed that the conformational structure of PBDA-a preferred to display zigzag conformation while PBDA-b display helix conformation. The mechanism of the polydiazocine synthesis is assumed to condensation polymerization proceeding by an unprecedented cyclization of the isocyanate with the neighboring acyl group, followed by the dimerization to form diazocine ring. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4694-4701