Halide perovskite nanocrystals hold promise for printable optoelectronic and photonic applications. Doping enhances their functionalities and is being investigated for substituting lead with environmentally friendlier elements. The most investigated dopant is Mn2+ that acts as a color center sensitized by the host excitons. The sensitization mechanism is far from understood and no comprehensive picture of the energy-transfer process has been proposed. Similarly, the role of shallow states, particularly abundant in defect tolerant materials, is still unknown. Here, we address this problem via spectroscopic studies at controlled excitation density and temperature on Mn:CsPbCl3 nanocrystals. Our results indicate a two-step process involving exciton localization in a shallow metastable state that mediates the thermally assisted sensitization of the Mn2+ emission, which is completely quenched for T < 200 K. At T ≤ 60 K …