The ester sulfonate anionic surfactants are a potentially valuable class of sustainable surfactants. The micellar growth, associated rheological changes, and the onset of precipitation are important consequences of the addition of electrolyte and especially multi-valent electrolytes in anionic surfactants. Small angle neutron scattering, SANS, has been used to investigate the self-assembly and the impact of different valence electrolytes on the self-assembly of a range of ester sulfonate surfactants with subtly different molecular structures. The results show that in the absence of electrolyte small globular micelles form, and in the presence of NaCl, and AlCl3 relatively modest micellar growth occurs before the onset of precipitation. The micellar growth is more pronounced for the longer unbranched and branched alkyl chain lengths. Whereas changing the headgroup geometry from methyl ester to ethyl ester has in general a less profound impact. The study highlights the importance of relative counterion binding strengths and shows how the surfactant structure affects the counterion binding and hence the micelle structure. The results have important consequences for the response of such surfactants to different operational environments.