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In this work, the evolution of dispersed droplets formation in a water-in-oil, W/O emulsion was observed using calorimetry technique. The emulsion was prepared by dispersing drop by drop of an aqueous phase into an oil continuous phase at room temperature using rotor-stator homogenizer. The droplets formation during: (1) formulation; (2) stabilization (3) and destabilization were observed using Differential Scanning Calorimertry, DSC. The samples were gently cooled-down below to its solid-liquid equilibrium temperature then heated back above the melting point to determine its solidification temperature. The energy released during the process was recorded in order to get information about the water droplet dispersion state. The mean droplet size distribution of the sample emulsion was correlated to its solidification temperature and the morphology was followed by optical microscopy. The results indicated that the calorimetry technique so far are a very good technique to characterize of W/O emulsion system