The film quality of perovskite absorber plays a fundamental role in determining the efficiency and stability of perovskite solar cells (PSCs), of which high crystallinity and low defect density are consistently persuaded. Here, a strategy using multifunctional additive of N,N′-Diallyl-L-tartardiamide (NDT) to produce high-quality perovskite film is proposed. The rich coordination and hydrogen bonding between NDT and perovskite effectively passivate trap states, improve film crystallinity, stabilize perovskite crystal structure and confine ions migration, resulting in enhancement of charge transport and suppression of nonradiative recombination. Consequently, compared with the control device (19.07 %), the NDT-modified devices achieve a champion efficiency of 21.71 % with negligible hysteresis as well as excellent air and light stability. This work presents a facile and effective approach via multifunctional molecular additive to achieve high-performance inverted (p-i-n) PSCs.