The hybrid evaporation/spin-coating route has been widely used for fabrication of highly efficient fully textured perovskite silicon tandem solar cells and is a promising route for upscaling. Nevertheless, fundamental aspects of the fabrication process such as the kinetics of perovskite crystallization and the influence of the environmental conditions remain uncertain. In this work, we investigate the individual stages of tandem-relevant 1.66 eV bandgap perovskite formation and map the structural evolution from the precursor to the perovskite phase until the degradation phase. We find that the kinetics of these transitions can be tuned by varying the humidity or the temperature during the annealing treatment. Specifically, increasing the relative humidity up to 50% elevates the reaction rate and results in improved perovskite quality. This is directly reflected in the solar cell power conversion efficiency with a 3%abs increment on average. While high annealing temperatures are found to promote large grain size growth and enhanced crystallinity, we observe that above 150 °C the remnant PbI2 precursor compromises film quality. Furthermore, the perovskite formation kinetics is fitted using the Johnson–Mehl–Avrami–Kolmogorov model. The Avrami constant is found in the range 0.66–0.87, indicating a diffusion-controlled one-dimensional growth process with an associated activation energy of 54.49 kJ/mol. Using in situ XRD, this work gives insights on key process parameters to ensure reproducible synthesis of high-quality perovskite films.