Dimension regulation and defect passivation are two key strategies for highly efficient and stable perovskite solar cell. Vapor deposition of perovskite is a toxic-solvent-free method for large-scale fabrication. However, without the assistance of solvent for crystal optimization, effective structural regulation and defect passivation become challenging. Here, detailed investigations on the structural evolution of perovskite thin film are carried out in sequential vapor deposition using mixed-vapor (R-NH3I/MAI). Correlation between electron donating ability of R-NH3I (BAI, PEAI, PMAI and ALI) molecule and the way of structural transition is established. It is found that RNH3I with stronger electron-donating ability promoted the phase transition from three-dimensional (3D) to twodimensional (2D) perovskite. Typically, the n value from 1 to 5 can be tuned by reaction time or component control using BAI with the strongest electron donating ability. R-NH3I with weak electron-donating ability suppresses the 3D to 2D transition, but enhances the defect passivation effect. The ALI with the weakest electron donating ability shows the best passivation effect, leading to the best device performance than that of the control 3D device, with PCE of 18.23% (0.045 cm2) and 15.48% (1 cm2) and the significantly improved stability. This study provides the evidence that the concept of Lewis acid-base reaction is applicable in vapor deposition, which provides us with the selection guide of R-NH3I molecules for structural design in vapor fabrication of perovskite thin film.