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Triple‐mesoscopic perovskite solar cells (PSCs) have attracted intensive attention due to the high stability, simple fabrication process, and low material cost. In this structure, the perovskite layer is hosted by a triple‐mesoscopic scaffold of TiO2/ZrO2/carbon, and thus the crystal quality is sensitive to the thermal annealing process. Typically, the annealing process is conducted in a petri dish, for which the solvent evaporation of the perovskite precursor is slowed down, but not controllable and designable. To control the solvent evaporation, annealing chambers are first designed with different shape and vapor releasing channels. Then, physical simulations are performed by a finite element method, and it is found out that the chamber with a crowned top and releasing channels on the bottom sides can realize homogeneous distribution of the solvent vapor. To verify the simulation results, chambers are fabricated by 3D printing technique, for which the printing deviation can be as low as 100 µm. By balancing the solvent evaporation and release, the optimal solvent evaporation is achieved of the perovskite precursor in the triple‐mesoscopic scaffold. This work offers a method to obtain homogeneous distribution of solvent vapor, and provides a new insight into understanding the influence of solvent evaporation during the thermal annealing process for PSCs. [ABSTRACT FROM AUTHOR]