AbstractCocoa powder quality is determined by its color, flavor, dispersion, and flow properties, which can be controlled via tempering. Design of a cocoa powder tempering profile, however, requires that the mechanism of cocoa butter crystallization in cocoa powder be fully understood. Low‐fat (8–12%) and high‐fat (20–24%) cocoas were sourced from two commercial manufacturers at varying degrees of alkalization and compared with two commercial cocoa butters. Unrefined paired cocoa powders and cocoa butters sampled from the hydraulic press were also evaluated. Isothermal crystallization kinetics and polymorphism of cocoa powders and cocoa butters were compared at 18, 21, and 24 °C using a direct time‐domain nuclear magnetic resonance method, differential scanning calorimetry, and x‐ray diffraction. Crystallization was also studied under dynamic tumbling conditions. It was found that cocoa butter in cocoa powder was nucleated by the cocoa powder matrix and transitioned to higher‐stability polymorphs more rapidly than bulk cocoa butters. High‐fat cocoas also exhibited enhanced crystallization kinetics relative to low‐fat cocoas, showing that differences in the cocoa microstructure may influence crystallization behavior. Notably, alkalization did not significantly affect the crystallization behavior of most cocoa powders. Finally, it was found that tumbling conditions led to crystallization of βV and that caking, especially of high‐fat cocoas, could be reduced by a static low‐temperature hold step prior to tumbling. Overall, these results demonstrated that crystallization of cocoa butter in cocoa powder is influenced both by the intrinsic attributes of the cocoa powder as well as the conditions of the tempering process.