In this study, single-nozzle electrospraying was used to prepare microencapsulated phase change materials. The effects of core/shell (n-hexadecane/polycaprolactone) mass ratios on the structure, morphology and thermal properties, were analyzed by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). A ratio about 50/50 was found as the most suitable to fabricate microcapsule with a narrow microcapsule sizes distribution, a complete core-shell structure and a smooth surface. Furthermore, the encapsulation efficiency in n-hexadecane reaches maximum at this ratio value. Finally, not only interesting latent heat can be obtained from these microcapsules, but also improved thermal stability of n-hexadecane.