Perovskite Solar Cells are a promising solar energy harvesting technology due to their low cost and high-power conversion efficiency. A high-quality perovskite layer is fundamental for a highly efficient perovskite Solar Cell. Utilizing a gas quenching process (GQP) can eliminate the need for toxic, flammable, and expensive anti-solvents in the preparation of perovskite layers. It is a promising candidate technology for large scale preparation of perovskite layers, as it can be easily integrated in a production line by coupling up-scalable techniques. The GQP removes the need for polar solvents in the precursor solution layer by using nitrogen flow, rather than extracting them with non-polar solvents. The crystallization dynamics in this process can be significantly different. In this study, we found that the quality of perovskite crystal from GQP is much more sensitive to Lewis base molecules (LBMs) in the precursor solution than it is in anti-solvents technology. Thus, the processing parameters of the LBMs in anti-solvents technology cannot be directly transferred to the GQP. An XRD and 1H NMR study explains the origin of the S-shaped J–V curves and how these LBMs hinder the reaction between PbI2 and monovelent cations.