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Hole‐collecting monolayers have greatly advanced the development of positive‐intrinsic‐negative perovskite solar cells (p‐i‐n PSCs). To date, however, most of the anchoring groups in the reported monolayer materials are designed to bind to the transparent conductive oxide (TCO) surface, resulting in less availability for other functions such as tuning the wettability of the monolayer surface. In this work, we developed two anchorable molecules, 4PATTI‐C3 and 4PATTI‐C4, by employing a saddle‐like indole‐fused cyclooctatetraene as a π‐core with four phosphonic acid anchoring groups linked through propyl or butyl chains. Both molecules form monolayers on TCO substrates. Thanks to the saddle shape of a cyclooctatetraene skeleton, two of the four phosphonic acid anchoring groups were found to point upward, resulting in hydrophilic surfaces. Compared to the devices using 4PATTI‐C4 as the hole‐collecting monolayer, 4PATTI‐C3‐based devices exhibit a faster hole‐collection process, leading to higher power conversion efficiencies of up to 21.7 % and 21.4 % for a mini‐cell (0.1 cm2) and a mini‐module (1.62 cm2), respectively, together with good operational stability. This work represents how structural modification of multipodal molecules could substantially modulate the functions of the hole‐collecting monolayers after being adsorbed onto TCO substrates. [ABSTRACT FROM AUTHOR]