In this paper, the role of the different structural isomers of the anionic surfactant sodium para-dodecyl benzene sulfonate, LAS, on surface adsorption and solution self-assembly has been studied. Using a combination of neutron reflectivity, NR, and small angle neutron scattering, SANS, the effect of mixing an isomer with a short symmetric hydrocarbon chain with one which has an asymmetric hydrocarbon chain on both the equilibrium surface adsorption behavior and the solution microstructure of the mixtures, both in the presence and absence of a divalent cation (Ca(2+)), has been investigated. In the absence of electrolyte, the LAS isomer mixtures form small charged globular micelles throughout the composition range studied. The micelle aggregation number increases with the increase in the asymmetric isomer content, reflecting an increase in the packing efficiency within the micelle. The addition of calcium ions promotes the formation of planar aggregates, as multilamellar vesicles, but only when the symmetric LAS isomer is the major component of the mixture. At a surfactant concentration just above the critical micelle concentration, CMC, and in the absence of electrolyte, the variation in the surface composition is close to the solution composition. Regular solution theory, RST, calculations show that this variation is also close to what is expected for ideal mixing. The addition of Ca(2+) ions induces a different surface behavior, resulting in the formation of multilayer structures at the interface throughout the entire composition range.