ABSTRACT Surfactant-oil-water systems in which the surface active substance is a mixture of carboxylic acid and its sodium salt (soap), exhibit emulsion property maps that are consistent with the phase behavior and the general emulsion phenomenology. However they present specific features such as an extended C+ multiple emulsion region and a skinked A+ W/O emulsion zone. In this case the aqueous phase pH drives the relative hydrophilicity of the acid/salt mixture at interface and plays the role of the most sensitive formulation variable. Studied systems contain C10 to C14 carboxylic acid, NaCl brine and a light distillation cut, as well as alcohols.