The petroleum industry produces thousands of barrels of oilfield waters from the initial stage driven by primary production mechanisms to the tertiary stage. These produced waters contain measurable amounts of oil-in-water emulsions, the exact amounts being determined by the chemistry of the crude oil. To meet strict environmental regulations governing the disposal of such produced waters, demulsification to regulatory permissible levels is required. Within the electric double layer theory, coupled with the analytical solutions to the Poisson−Boltzmann Equation, continuum electrostatics approaches can be used to describe the stability and electrokinetic properties of emulsions. In the literature, much of the surface charge density and zeta potential relationship to emulsion stability has been confined to systems with less salinity. In this paper, we have exploited the theoretical foundations of the electric double layer theory to carry out theoretical evaluations of emulsion salinity based on zeta potential and surface charge density calculations. Most importantly, our approaches have enabled us to extend such theoretical calculations to systems of the higher salinity characteristic of oil-in-water emulsions found in oilfield-produced waters, based on crude oil samples from the literature with varying surface chemistry. Moreover, based on the definition of acid crude oils, our choice of samples represents two distinct classes of crude oils. This approach enabled us to evaluate the stability of emulsions associated with these produced oilfield waters in addition to predicting the potential of demulsification using demulsifiers. Given that the salinity range of this study is that encountered with the vast majority of produced oilfield waters, the findings from our theoretical predictions are perfect guides as far as emulsion stability is concerned.