Surface defects and the susceptibility of the perovskite absorber in the presence of moisture result in poor long-term device stability, eventually constricting its commercialization. To overcome these detrimental issues, herein we designed, synthesized, and introduced a multifunctional organic small molecule (GS1), configured upon triphenylamine linked with phenothiazine via π-linker vinylene-thiophene-vinylene, between the dual-cation perovskite absorber and the hole transport layer (HTL) spiro-OMeTAD. The incorporated interface material's unique extended conjugation and electron-donating ability, along with optimum energy level alignment, benefits in the hole extraction. Undercoordinated lead cations in the perovskite lattice structure were successfully passivated by the donation of lone pairs of electrons present in the GS1 molecule, and the superior film-forming properties significantly influence the charge carrier dynamics. The device composed of the GS1 hole-transporting interfacial layer delivers a lower leakage current, high shunt resistance, and reduced trap-state density as compared to the pristine device. Consequently, the device J−V parameters like short circuit current density (J sc ), fill factor (FF), and power conversion efficiency (PCE) show considerable improvement as compared to the pristine device. Superior thermal stability and hydrophobicity rendered by the GS1 molecule assist in preventing moisture ingress, which results in improved stability under high relative humidity conditions.