Athabasca bitumen contains 1-2 wt % naphthenic acids, similar to 18 wt % asphaltenes, and similar to 40 wt % resins, all of which can stabilize bitumen-based water-in-oil (W/O) emulsions. The asphaltenes fraction is generally considered as the most important fraction in stabilization of W/O emulsions. It is also known that, once the asphaltenes are removed from a crude oil, the oil ability to form stable W/O emulsions is decreased. In conventional bitumen extraction, sodium hydroxide is used as a process aid. Therefore, naphthenic acids in bitumen can be converted to their sodium salts. Commercial sodium naphthenate (SN) is known to stabilize both oil-in-water and water-in-oil emulsions. The questions are whether SN precipitates with the asphaltenes and, if it does, whether it is SN that is responsible for emulsion stabilization rather than asphaltenes. Asphaltenes precipitation experiments were conducted with and without the addition of SN. It was found that SN does not co-precipitate with asphaltenes and likely reports into the maltenes fraction. Emulsion stabilization ability of SN was lower than that of asphaltenes. Our results indicate that the leading role in the stabilization of W/O emulsions is likely played by a not yet identified subfraction of asphaltenes. It is unlikely that asphaltenes as a whole or this subfraction contains SN.