Microencapsulated phase-change-materials (PCMs) incorporated in cementitious grout can be used as a source of energy in an underground thermal energy storage system. Differential scanning calorimetry (DSC) is a widely used technique to measure the latent heat or specific heat of PCM-embedded cementitious materials. However, using milligram sample sizes (as required by DSC) of a cementitious material fails to represent the actual scale of cementitious components. This is the reason why, in the present paper, non-isothermal heat conduction microcalorimetry (MC) was evaluated as a tool for determining the thermal properties of PCM-embedded grout as well as pure PCM (three PCMs were used). An MC experimental protocol (using both single and 5–6 temperature cycles) was developed and used to measure latent heat and melting and crystallization temperatures, which were in good agreement with those reported for pure PCMs by the producers. In addition, the specific heats of the PCM-containing grout also agreed with measurements using the hot disk technique. Overall, the results show that the MC technique can be used as a potential standard method in determining thermal processes in complex systems, such as in PCM-embedded cementitious systems, where a large sample size is needed to represent the material.