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Solution-processed perovskite films generally possess small grain sizes and high density of grain boundaries, which intensify non-radiative recombination of carriers and limits the power conversion efficiency (PCE) of solar cells. In this study, we report the room-temperature ripening enabled by the synergy of hygroscopic salts and moisture in air for efficient hole-conductor-free printable mesoscopic perovskite solar cells (p-MPSCs). Treating perovskite films with proper hygroscopic salts in damp air induces obvious secondary recrystallization, which coarsens the grains size from hundreds of nanometers to several micrometers. It's proposed that the hygroscopic salt at grain boundaries could absorb moisture and form a complex which could not only serve as mass transfer channel but also assist in the dissolution of perovskite grains. This activates mass transfer between small grains and large grains since they possess different solubilities, and thus ripens the perovskite film. Consequently, p-MPSCs treated with the hygroscopic salt of NH4SCN show an improved power conversion efficiency of 20.13% from 17.94%, and maintain >98% of the initial efficiency under maximum power point tracking at 55±5°C for 350 hours., (© 2024 Wiley‐VCH GmbH.)