In order to further promote the commercial application of perovskite solar cells (PSCs), it is particularly important to fabricate devices in the ambient air condition. Herein, we explore a simple method to reproduce high-efficiency and stable PSCs using the one-step anti-solvent deposition conducted in the full ambient air. NH4Ac (ammonium acetate), which is green and environmentally friendly, is first introduced into an anti-solvent (ethyl acetate) to enhance the photovoltaic performance and stability of devices. NH4+ causes the intermediate phase to undergo a process of cation exchange, thereby delaying crystallization. Ac– makes the additive and A-site cation form hydrogen bonds, which in turn makes the intermediate phase more stable. The dual effects of NH4+ and Ac– delay the crystallization of the perovskite film, reduce the density of defect states, and decrease the non-radiative recombination of carriers. By optimizing the concentration of NH4Ac, a champion power conversion efficiency (PCE) of 20.41% and an average PCE of 19.46 ± 0.64% are achieved, which is currently one of the highest efficiencies in fabricating PSCs under the full ambient air condition. Furthermore, the corresponding PSCs without encapsulation can maintain 82% of its initial PCE when stored in full ambient air condition (30–40% RH) for 30 days.