Interfacial trap-assisted nonradiative recombination hampers the development of metal halide perovskite solar cells (PSCs). Herein, we report a rationally designed universal passivator to realize highly efficient and stable single junction and tandem PSCs. Multiple defects are simultaneously passivated by the synergistic effect of anion and cation. Moreover, the defect healing effect is precisely modulated by carefully controlling the number of hydrogen atoms on cations and steric hindrance. Due to minimized interfacial energy loss, L-valine benzyl ester p-toluenesulfonate (VBETS) modified inverted PSCs deliver a power conversion efficiency (PCE) of 26.28% using vacuum flash processing technology. Moreover, by suppressing carrier recombination, the large-area modules with an aperture area of 32.144 cm² and perovskite/Si tandem solar cells coupled with VBETS passivation deliver a PCE of 21.00% and 30.98%, respectively. This work highlights the critical role of the number of hydrogen atoms and steric hindrance in designing molecular modulators to advance the PCE and stability of PSCs.