Nano-emulsions consist of fine oil-in-water dispersions, having droplets covering the size range of 100-600 nm. In the present work, nano-emulsions were prepared using the spontaneous emulsification mechanism which occurs when an organic phase and an aqueous phase are mixed. The organic phase is an homogeneous solution of oil, lipophilic surfactant and water-miscible solvent, the aqueous phase consists on hydrophilic surfactant and water. An experimental study of nano-emulsion process optimisation based on the required size distribution was performed in relation with the type of oil, surfactant and the water-miscible solvent. The results showed that the composition of the initial organic phase was of great importance for the spontaneous emulsification process, and so, for the physico-chemical properties of the obtained emulsions. First, oil viscosity and HLB surfactants were changed, alpha-tocopherol, the most viscous oil, gave the smallest droplets size (171 +/- 2 nm), HLB required for the resulting oil-in-water emulsion was superior to 8. Second, the effect of water-solvent miscibility on the emulsification process was studied by decreasing acetone proportion in the organic phase. The solvent-acetone proportion leading to a fine nano-emulsion was fixed at 15/85% (v/v) with EtAc-acetone and 30/70% (v/v) with MEK-acetone mixture. To strength the choice of solvents, physical characteristics were compared, in particular, the auto-inflammation temperature and the flash point. This phase of emulsion optimisation represents an important step in the process of polymeric nanocapsules preparation using nanoprecipitation or interfacial polycondensation combined with spontaneous emulsification technique.