Oil/water (O/W) nano-emulsions have been formed in the system water/C16E6/mineral oil by the phase inversion temperature (PIT) method. The relation between the phase equilibria observed at the hydrophilic-lipophilic balance (HLB) temperature or the PIT (i.e., the nature, number, and relative volume fractions of the involved phases), the droplet sizes, and polydispersities of the resulting emulsions have been determined. Milky white emulsions were obtained when, at the HLB temperature, a three-phase equilibrium formed by water (W), shear-birefringent microemulsion (D), and oil (O) was observed. However, bluish transparent O/W nano-emulsions with droplet sizes as low as 40 nm were formed in a narrow range of oil-to-surfactant ratios in which a D or W + D phases were the initial equilibrium phases. In the W + D equilibria, droplet sizes were independent from the water content, indicating that nanodroplet formation is mainly controlled by the structure of the D phase. These results suggest that the main requirement for bluish transparent O/W nano-emulsion formation is the complete solubilization of the oil component in a bicontinuous microemulsion, independent of whether the initial phase equilibrium is single or multiphase.