P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. We report a thermally robust hole-selective layer comprised of nickel oxide (NiOx) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiOx/perovskite interface. The energetic alignment and favorable contact and binding between NiOx/MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53-electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.