•A new POP film has been developed by electrochemical polymerization.•The carbazolyl triphenylethylene derivative is using as building block for the film.•The cross-linked POP film had smooth surface morphology and 3D nanostructures.•The PCE of POP film based PSCs showed a 13% enhancement.A facile and controllable electrochemical polymerization of porous organic polymers (POP) film using carbazolyl triphenylethylene derivative (TPCz) as building block for the applications in polymer solar cells(PSCs) was developed. The POP film is an interlocked network film of poly-TPCz (designated as PTPCz) which has smooth surface morphology and porous nanostructures. The film can increase the work function (WF) of the anode of PSCs, the contact with the active layer, and enhance hole-extraction process. By using PEDOT:PSS/PTPCz instead of PEDOT:PSS as the anode interlayer, the optimized PSCs shows a 13% enhancement in power conversion efficiency (PCE) which is 8.54%. These results indicate the potential of electrochemical synthesized POP film as efficient interlayer for PSCs.A porous organic polymer (POP) film using carbazolyl triphenylethylene derivative (TPCz) as building block is applied in efficient interlayers for polymer solar cells(PSCs).Download high-res image (215KB)Download full-size image