The nucleation and growth of organic–inorganic hybrid perovskite films induced by the molar ratio of precursor components and their role in optoelectronic performance are investigated. Lead iodide (PbI₂), methylammonium acetate (MAAc) and methylammonium iodide (MAI) mixed in different ratios were used as starting precursors for active layer deposition. While all the as cast films showed the presence of a precursor intermediate (PbI_x·MAAc·MAI), the films derived from 1 : 1 : 1 and 1 : 0.5 : 1 ratios also exhibited crystallization of the perovskite (CH₃NH₃PbI₃) phase during the spin coating process. The nucleation and crystallization of the perovskite phase in films derived from the equimolar precursor ratio were found to be the key to growing larger, smoother and single crystalline grains along the thickness leading to higher carrier lifetimes. Perovskite solar cells fabricated utilizing such a morphology showed a much higher power conversion efficiency irrespective of the active layer thickness. Furthermore, methyl ammonium bromide based perovskite light emitting diodes were also fabricated using the aforementioned equimolar precursor ratio which exhibited superior device performance compared to diodes with active layers derived from other precursor ratios. This work highlights a facile deposition technique and growth mechanism to attain reproducible, low cost and high-performance perovskite optoelectronic devices.