The kinetics of spontaneous emulsification is investigated on aqueous pendant drops in paraffin oil. Optical microscopy in transmission mode is used for high-spatial-resolution image recording. The influence of a lipophilic surfactant (Span 80) and two water-soluble surfactants (CTAB and SDS) is investigated. As time runs, the drop interface turns opaque due to the formation of microstructures associated with spontaneous emulsification. The time evolution of this phenomenon is shown to depend upon temperature and surfactant concentration, which leads to an overall shrinkage due to gradual water uptake and transport into paraffin oil. Spontaneous emulsification kinetics depends upon the chemical composition. Higher concentrations of Span 80 and CTAB (resp. SDS) are shown to promote (resp. hinder) water transport. This work provides new insights into the understanding of spontaneous emulsification when combining the properties of non-ionic and ionic surfactants.