Black phase CsPbI3 is attractive for optoelectronic devices, while usually it has a high formation energy and requires an annealing temperature of above 300 °C. The formation energy can be significantly reduced by adding HI in the precursor. However, the resulting films are not suitable for light-emitting applications due to the high trap densities and low photoluminescence quantum efficiencies, and the low temperature formation mechanism is not well understood yet. Here, we demonstrate a general approach for deposition of γ-CsPbI3 films at 100 °C with high photoluminescence quantum efficiencies by adding organic ammonium cations, and the resulting light-emitting diode exhibits an external quantum efficiency of 10.4% with suppressed efficiency roll-off. We reveal that the low-temperature crystallization process is due to the formation of low-dimensional intermediate states, and followed by interionic exchange. This work provides perspectives to tune phase transition pathway at low temperature for CsPbI3 device applications.