Self-diffusion in a bitumen emulsion was studied by 1H NMR. The emulsion forms two phases: continuous and dispersed. The continuous aqueous phase contains mainly water, with the energy of activation of the diffusion process equal to that of bulk water, while its diffusivity is smaller than that of bulk water by a factor of 2. The dispersed phase consists of bitumen droplets containing confined water, whose dynamics is characterized by a fully restricted diffusion regime in cavities with sizes of ∼0.11 μm. Therefore, the studied bitumen emulsion can be described by a model of a complex multiple emulsion of the water/oil/water (WOW) type. The suggested model does agree well with data from 1H NMR spectroscopy and diffusometry of the bitumen emulsion doped with paramagnetic MnSO4(aq) as well as with an additional 1H NMR study of the emulsion structure, in which emulsion stability was compromised by freezing at 253 K.