Abstract Two new thiophene-substituted porphyrins and their zinc complexes were synthesized and electropolymerized via thiophene units on different electrode surfaces. Electrochemical characterizations show that the resultant polythiophenemetalloporphyrin hybrid materials are highly electroactive and exhibit remarkable higher electrochemical stability. Interestingly, they exhibit a charge-trapping effect. A mechanism for the observed charge-trapping phenomenon was proposed and supported by using model compounds. The deposited polymer films on different electrode surfaces exhibit a homogeneous morphology and possess good processability (soluble in polar solvents such as DMSO or DMF). Besides electrochemical method, UV/vis, NMR, FTIR, TEM and SEM were employed to characterize the new hybrid material.