Mixed aquo-organic solvents are used in chemical, industrial, and pharmaceutical processes along with amphiphilic materials. Their fundamental studies with reference to bulk and interfacial phenomena are thus considered to be important, but such detailed studies are limited. In this work, the interfacial adsorption of sodium dodecylsulfate (SDS, C12H25SO4-Na+) in dioxane water (Dn-W) and methanol water (Ml-W) media in extensive mixing ratios along with its bulk behavior have been investigated. The solvent-composition-dependent properties have been identified, and their quantifications have been attempted. The SDS micellization has been assessed in terms of different solvent parameters, and the possible formation of an ion pair and triple ion of the colloidal electrolyte, C12H25SO4-Na+ in the Dn-W medium has been correlated and quantified. In the Ml-W medium at a high volume percent of Ml, the SDS amphiphile formed special associated species instead of ion association. The formation of self-assembly and the energetics of SDS in the mixed solvent media have been determined and assessed using conductometry, calorimetry, tensiometry, viscometry, NMR, and DLS methods. The detailed study undertaken herein with respect to the behavior of SDS in the mixed aquo-organic solvent media (Dn-W and Ml-W) is a new kind of endeavor.