The quality of the perovskite active layer directly impacts the photovoltaic performance of perovskite solar cells (PSCs). Unfortunately, perovskite films produced through solution methods often have a significant number of defects on their surface, which lead to a substantial degradation in the performance of devices. For this reason, a multifunctional additive 2-(trifluoromethyl) benzimidazole (TFMBI) is introduced into perovskite films. Based on the Lewis acid/base coordination principle, the TFMBI double site cooperatively passivates surface defects, inhibiting carrier non-radiative recombination. Simultaneously, the hydrophobic solid group (-CF 3 ) of TFMBI covers the surface, establishing a moisture-oxygen barrier and improving the environmental stability of the devices. In consequence, the power conversion efficiency (PCE) of TFMBI-modified PSCs reached 23.16%, significantly higher than the pristine one with a PCE of 20.62%. Additionally, the unencapsulated target device retained 90.32% of its initial PCE even after being reserved in the air with a relative humidity of 20-30% for 60 days.