The main problems holding back inverted perovskite solar cells (PSCs) are poor crystal formation and too many defects inside the perovskite layer. We address both issues by introducing 4-aminobutylphosphonic acid, which effectively releases residual tensile stress and passivates film defects, leading to enhanced efficiency and stability. We report 4-aminobutylphosphonic acid as a multifunctional additive where the phosphonic acid (–PO3H2) and amine (–NH2) groups coordinatively passivate undercoordinated Pb2+ and I− vacancies, as supported by GIXRD measurements showing 64% reduction in residual tensile stress, and time-resolved photoluminescence shows enhanced carrier lifetime. The optimized devices achieve a champion power conversion efficiency (PCE) of 24.1% and retain 85% of its initial PCEs after 840 h under 1-sun illumination at 65 °C. This molecular engineering approach provides a facile route to concurrently boost efficiency and stability in inverted PSCs.