We found for the first time a new origin of selection of perovskite crystallization pathways from DMF solutions containing MAI and PbI2 to present here a comprehensive study of a full set of essential intermediate phases determining the perovskite's morphology. For all three discovered structurally different intermediate phases forming at a given precursor ratio, we refined their crystal structures. by synchrotron X-ray radiation and investigated dynamics and phase assemblage in the course of decomposition. As a result, we revealed a clear correlation between the composition of the intermediate phases, peculiarities of their crystal structure, and the morphology of the final perovskite films. Using the DFT method we, calculated formation enthalpies of these intermediate phases and explained the preferential precipitation of DMSO-adduct rather than DMF-adduct in an antisolvent approach. This finding opens up a possibility of design-on-demand of perovskite materials using simple soft chemistry approaches.