Although the surface tension of complex mixtures determines the fate of many important natural processes, the property is notoriously difficult to interpret. Here we announce a new method that successfully predicts the surface tension of two synthetic and one biological polyelectrolyte/surfactant mixtures in the phase-separation region after dynamic changes in the bulk phase behavior have reached completion. The approach is based on the nonequilibrium framework of a lack of colloidal stability of bulk complexes in compositions around the charge match point of the oppositely charged components and requires as input parameters only the surface tension isotherm of the pure surfactant and some bulk measurements of the mixtures; no surface measurements of the mixtures are required. The complexity of the problem is reduced to a single empirical equation. This simplification in our understanding of the surface properties of strongly interacting mixtures involving macromolecules can lead to the optimization of applications involving synthetic polymers and biomacromolecules such as DNA at surfaces.