The ability to passivate defects and modulate the interface energy-level alignment (IEA) is key to boost the performance of perovskite solar cells (PSCs). Herein, we report ar obust route that simultaneously allows defect passivation and reduced energy difference between perovskite and hole transport layer (HTL) via the judicious placement of polar chlorine-terminated silane molecules at the interface. Density functional theory (DFT) points to effective passivation of the halide vacancies on perovskite surface by the silane chlorine atoms.A ni ntegrated experimental and DFT study demonstrates that the dipole layer formed by the silane molecules decreases the perovskite work function, imparting an Ohmic character to the perovskite/HTL contact. The corresponding PSCs manifest anearly 20 %increase in power conversion efficiency over pristine devices and am arkedly enhanced device stability.A ss uch, the use of polar molecules to passivate defects and tailor the IEA in PSCs presents apromising platform to advance the performance of PSCs.