This study introduced a robust and promising approach to fabricate highly stable phase change material (PCM) emulsions consisting of n-tetradecane as a dispersed phase and a mixture of meso-2,3-butanediol (m-BDO) and water as a continuous phase. We showed that amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) block copolymers assembled to form a flexible but tough polymer membrane at the interface during phase inversion from water-in-oil emulsion to oil-in-water emulsion, thus remarkably improving the emulsion stability. Although the incorporation of m-BDO into the emulsion lowered the phase changing enthalpy, it provided a useful means to elevate the melting temperature of the emulsions near to 15 degrees C. Interestingly, supercooling was commonly observed in our PCM emulsions. We attributed this to the fact that the PCM molecules confined in submicron-scale droplets could not effectively nucleate to grow molecular crystals. Moreover, the presence of m-BDO in the continuous phase rather dominated the heat emission of the emulsion system during freezing, which made the supercooling more favorable.