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Ultraviolet‐induced degradation has emerged as a critical stability concern impeding the widespread adoption of perovskite solar cells (PSCs), particularly in the context of phase‐unstable wide‐band gap perovskite films. This study introduces a novel approach by employing a fully aromatic carbazole‐based self‐assembled monolayer, denoted as (4‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)phenyl)phosphonic acid (MeO‐PhPACz), as a hole‐selective layer (HSL) in inverted wide‐band gap PSCs. Incorporating a conjugated linker plays a pivotal role in promoting the formation of a dense and highly ordered HSL on substrates, facilitating subsequent perovskite interfacial interactions, and fostering the growth of uniform perovskite films. The high‐quality film could effectively suppress interfacial non‐radiative recombination, improving hole extraction/transport efficiency. Through these advancements, the optimized wide‐band gap PSCs, featuring a band gap of 1.68 eV, attain an impressive power conversion efficiency (PCE) of 21.10 %. Remarkably, MeO‐PhPACz demonstrates inherent UV resistance and heightened UV absorption capabilities, substantially improving UV resistance for the targeted PSCs. This characteristic holds significance for the feasibility of large‐scale outdoor applications. [ABSTRACT FROM AUTHOR]