The encapsulation of phase change materials (PCMs) into the micropores of an ordered polymer film was investigated. Paraffin wax and high density polyethylene wax were infiltrated successfully into extruded films of the ordered polymer PBZT by a solvent exchange technique to yield microcomposites with PCM levels on the order of 40 volume percent. These microcomposite films exhibit excellent mechanical stability under cyclic freeze-thaw conditions. However, their thermal energy storage capacities, as characterized by differential scanning calorimetry, decrease significantly following freeze-thaw cycling. It appears that the ultrastructure of the PBZT and the thinness of the film (which results in high cooling rates during freeze-thaw cycling) promote the retention of the amorphous form of the PCM rather than the crystalline form. Since the amorphous form of the PCM does not contribute to the latent heat of fusion, the heat storage capacity of the microcomposite is reduced.