The critical electric field (cef) technique has been utilized to measure the stabilities of a variety of water-in-model oil and petroleum emulsions. The cef method allows for a fast, reproducible, and quantitative gauge of emulsion stability. Here, we have used cef to measure the stability of water-in-heptane-toluene-asphaltene emulsions and confirmed the importance of solvation of asphaltenes and the state of asphaltene aggregation to emulsion stability. Emulsion stability increased with the concentration of soluble asphaltenes near the point of precipitation. Droplet sizes were measured with optical microscopy in order to calculate interfacial areas and film thicknesses. It was found that film thickness increased with asphaltene concentration up to the solubility limit, above which increased concentration had little effect, and cef increased with interfacial film thickness up to a monolayer coverage of asphaltene aggregates, above which film thickness had a much smaller effect. These findings were applied to a cef investigation of water-in-petroleum emulsions to develop correlations of the stability of water-in-crucle oil emulsions. A strong correlation (coefficient = 0.95) was found for cef with the product of asphaltene concentration and the difference in hydrogen to carbon atomic ratios of the asphaltenes and petroleum solvent. The development of a kinetic model and its fit to experimental data revealed the effects of asphaltene chemistry, solvency, and resin concentration on the adsorption and consolidation of emulsion stabilizing interfacial films.