The aim of this work was to investigate the phase behaviour and the structure of the n-hexane/water emulsions based on a nonionic, nontoxic and biocompatible surfactant, Tween 80. This system is of interest for new pharmaceutical techniques based on supercritical fluids to form nano- and encapsulated particles. However, it showed a lack of stability denoted by large areas of macroemulsion. For this reason, the effect of additives (alcohols and brine) and external variables (temperature) were explored. The replacement of water by brine caused negligible impact due to the nonionic character of Tween 80. On the contrary, the presence of an alcohol (ethanol or 1-butanol) enhanced the solubility of the surfactant in the oil phase and decreased the mixture viscosity, resulting in improved surface activity. Similar results were obtained by raising the temperature until the cloud point was reached (60°C). With these modifications, microemulsions at relatively low concentrations of surfactant (around 30%) and within a broad interval of compositions could be obtained, widening their possible use in pharmaceuticals manufacturing (such as controlled drug delivery, enzymatic reactions, or excipient processing). The understanding of the surfactant performance could be further used to substitute the n-hexane by a greener solvent, such as supercritical CO₂.