The perovskite phase of cesium lead iodide (α-CsPbI3 or "black" phase) possesses favorable optoelectronic properties for photovoltaic applications. However, the stable phase at room temperature is a nonfunctional "yellow" phase (δ-CsPbI3). Black-phase polycrystalline thin films are synthesized above 330 °C and rapidly quenched to room temperature, retaining their phase in a metastable state. Using differential scanning calorimetry, it is shown herein that the metastable state is maintained in the absence of moisture, up to a temperature of 100 °C, and a reversible phase-change enthalpy of 14.2 (±0.5) kJ/mol is observed. The presence of atmospheric moisture hastens the black-to-yellow conversion kinetics without significantly changing the enthalpy of the transition, indicating a catalytic effect, rather than a change in equilibrium due to water adduct formation. These results delineate the conditions for trapping the desired phase and highlight the significant magnitude of the entropic stabilization of this phase.