Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. In this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH3NH3PbI3) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI2 film, intercalating within the PbI2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored.Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.