Novel ladder-type polymers with diazocine units, namely polydiphenyldibenzo[1,5]diazocine (PBD) and polydimethoxyphenyldibenzo[1,5]diazocine (PMBD), were successfully prepared for molecular actuator by one-pot polymerization method. The structure of polydiaryldibenzo[1,5]diazocines was confirmed by NMR and FTIR. The molecular weights and molecular weight distributions of the polydiaryldibenzo[1,5]diazocines were characterized by GPC analysis. Cyclic voltammogram (CV) studies revealed that the redox behavior be reversible in one-electron transfer process. Moreover, molecular conformation calculations using the density functional theory method (DFT) showed that both PBD and PMBD prefer to display zigzag conformation and further suggest that the average percent dimensional change is 14.6 in the one-electron transfer process. These polymers with ladder-type structure show good solubility, which are very different from conventional ladder-type polymers, such as polypyrrole and polythiophene. Both of them can be dissolved well in common organic solvents, such as CHCl3, and THF. Studies of the polymers will afford us with novel materials to fabricate device using an electrochemical actuator.