Self-assembled monolayers (SAMs) have significantly contributed to the advancement of hole transporting materials (HTMs) for inverted perovskite solar cells (PSCs). However, uneven distribution of SAMs on the substrate largely decreases the PSC performance, especially for large-scale devices. Herein, the first spiro-type SAM, termed 4PA-spiro, with an orthogonal spiro[acridine-9,9′-fluorene] as the skeleton and phosphonic acid as the anchoring group were proposed. Compared to the reference 4PACz, the twisted configuration with larger steric hindrance of 4PA-spiro inhibited the intermolecular aggregation, enabling a uniform and homogeneous anchoring on the substrate. Moreover, the suitable highest occupied molecular orbital (HOMO) level of 4PA-spiro is beneficial in promoting hole extraction and reducing charge non-radiative recombination. As a result, compared to 4PACz with a power conversion efficiency (PCE) of 22.10%, the 4PA-spiro-based PSCs exhibited a superior PCE of 25.28% (certified 24.81%, 0.05 cm2), along with excellent long-term stability. More importantly, 4PA-spiro-enabled larger-area PSCs and modules achieved PCEs of 24.11% (1.0 cm2) and 21.89% (29.0 cm2), respectively, one of the highest PCEs for inverted PSC modules, providing an effective SAM candidate for the commercialization of efficient, stable and large-scale inverted PSCs.