Addressing the global demand for clean energy, perovskite solar cells (PVSCs) have emerged as one of the promising candidates. However, ensuring the stability of PVSCs under various environmental factors remains a critical issue for commercialization. Various ionic functionalities are incorporated into perylene diimide (PDIN) derivatives for altering the work function of aluminum electrodes. Well-known amino N-oxide terminal (PDIN-O), and quaternary ammonium salts (PDIN-Br and PDIN-I) were applied as cathode interlayer (CIL) materials in inverted PVSCs. Within the PDIN derivatives, PDIN-I stands out for its superior electron injection effectiveness, minimized energy losses, and enhanced interface contacts, resulting in an optimal device efficiency of 15.9 %. The research emphasizes the role of efficient interlayer engineering in enhancing layer contact and coverage, inhibiting moisture permeation, and improving device stability. PDIN derivatives emerge as eco-friendly alternatives, offering promising prospects for stable and high-performance inverted PVSCs.