Organic-inorganic hybrid perovskite solar cells (PSCs) have emerged as a promising candidate for next-generation solar cells. However, the limited stability of PSCs hampers their practical applications. In this work, for the first time, a functionalized π-conjugated ionic liquid crystal (ILC), 4'-(N,N,N-trimethyl ammonium bromide hexyloxy)-4-cyanobiphenyl (6CNBP-N), is developed as a novel chemical additive to obtain CH3NH3PbI3 (MAPbI3) PSCs with high efficiency and excellent moisture stability. This 6CNBP-N ILC possesses the characteristics of ionic liquids and liquid crystals. The inclusion of the 6CNBP-N ILC can effectively improve the quality and stability of perovskite films, reduce the trap-state densities, and promote the carrier transport induced by the cyano group (C≡N), a rod-like π-conjugated biphenyl mesogenic unit and quaternary alkylammonium cations (R4N+) in 6CNBP-N. Through this functionalized ILC engineering strategy, the power conversion efficiency (PCE) of PSCs is greatly increased from 18.07% for the control PSC to 20.45% for the PSC with 6CNBP-N along with the depressed hysteresis effect and enhanced moisture stability of PSCs. Our work provides a new strategy for designing functionalized additives for high-performance PSCs.