Three alloys, single-phase Cr2Hf, a two-phase alloy consisting of Cr solid solution and Cr2Hf, and a two-phase alloy consisting of Hf solid solution and Cr2Hf were cast and heat treated. The C14-to- C15 transformation of the Laves phase, Cr2Hf was studied as a function of heat treatment. According to the existing phase diagram, the Cr2Hf phase exhibits a C14 structure at elevated temperature but transforms to the C15 structure at lower temperatures. Such transformations are known to be extremely sluggish. In the present study, the Cr2Hf phase was found to retain the C14 structure at room temperature in all three compositions in the cast or cast and forged conditions; upon subsequent heat-treatment at various temperatures and time-at-temperatures, however, the C14 structure decomposes to a variety of higher order structures including the 16H, 10H, and 4H structures. These superstructures can be viewed as containing various percentages of the cubic and hexagonal stacking. The C15 structure was not observed for any of the conditions considered.