The performance of perovskite solar cells is largely enhanced by modifying the energy match of electrodes with coupled 2D interfacial layers. The V OC is about 0.17 V increased to 1.135 V and 1.176 V for the CH 3 NH 3 PbI 3 and CH 3 NH 3 PbI 2.5 Br 0.5 based devices, respectively. The PCE of the PEDOT:PSS based p–i–n solar cells is up to 19.14%.