This study proposes a hybrid SAM interface engineering strategy to address the issue of interface hole transport potential barriers caused by HOMO level mismatch in MeO-2PACz self-assembled monolayers in trans perovskite solar cells. By combining MeO-2PACz with Me-4PACz, which has a larger dipole moment, in a specific ratio, the energy level arrangement and defect passivation ability of the nickel oxide hole transport layer are optimized. Experiments have shown that when the volume fraction of Me-4PACz is 10%, the M-SAM/NiOx composite layer can significantly improve the interface charge extraction efficiency and induce the formation of a dense crystal structure in perovskite films. Based on this, the p-i-n structured PSCs prepared achieved an open circuit voltage of 1.079 V, a short-circuit current density of 24.23 mA/cm2, and a fill factor of 0.79. The photoelectric conversion efficiency increased from 18.7% to 20.76%.