The thermal conductivity of phase change materials (PCMs) during phase transitions is of great significance to the evaluation of the thermal performance of energy-saving buildings. Based on the transient plane source method, a method for measuring the effective thermal conductivity of PCM composites was proposed, by which the variations in effective thermal conductivity with liquid fraction and temperature during phase transitions can be obtained. The correctness of the proposed method was verified through matched simulation experiments. Three kinds of PCM samples were prepared for experimental measurement on the basis of the direct incorporation method, and the volume proportions of decanoic acid to gypsum were set to 10%, 12%, and 15%. The phase transition regions and latent heat values of these PCM samples were measured using the differential scanning calorimetry technique. Results showed that the effective thermal conductivity of the PCM first increased and then decreased during the phase transition. As the fraction of PCM content increased, the phase transition regions gradually expanded, and the effective thermal conductivity changed more drastically. The good measurement repeatability demonstrated the feasibility of this method for measuring the effective thermal conductivity of composites during phase transition.