The release of tetradecane from a multiple emulsion of the type tetradecane/water/hexadecane was studied experimentally using the differential scanning calorimetry technique. The kinetics of the tetradecane release was measured for three formulations containing different concentrations of hydrophilic surfactant (2%, 4%, and 7%). A new mass transfer model derived from the shrinking core model was developed. The values of the model parameters deduced from the least-squares fittings led to the determination of the tetradecane diffusivity. Thus, the preponderant mechanism of mass transfer was proved to be micellar diffusion and not molecular diffusion. This conclusion was confirmed by considering the effect of the change in the hydrophilic surfactant concentration.