Abstract Along with the growing popularity of the p‐i‐n structure, bathocuproine (BCP) is increasingly recognized as a crucial buffer layer between the electron transport layer and electrode with the role of mitigating Schottky contact and enhancing performance. However, the chemical structure and role of its functional groups have not been thoroughly elucidated. This study introduces a novel modification of BCP in perovskite solar cells (PSCs) by altering functional groups to optimize their geometrical molecular structures and electronic properties. The substitution of aromatic phenyl and p‐tolyl groups to 2,9‐position on the BCP is highly effective in increasing the planarity of the conjugated backbone and protecting the reactive nitrogen atoms of the phenanthroline core, thereby improving charge transport and device stability. Experimental analyses, including electrostatic force microscopy, impedance spectroscopy, and photoluminescence, reveal that the modified BCP significantly enhances charge transport, reduces recombination losses, and markedly improves the structural stability of PSCs, leading to prolonged device lifetimes. The findings highlight the potential of structurally optimized BCP derivatives as a critical component in advancing high‐efficiency and durable PSCs.