The addition of [2.2.2]cryptand (C222) to sodium dodecyl sulfate (SDS) micelles in aqueous solution is studied by small-angle neutron scattering (SANS): Hydrogenated and perdeuterated SDS micelles with 8% (wt/wt) concentration have been studied in the presence of 0.5, 1.0, and 1.5 Mole ratio C222/surfactant. SANS analysis was performed using a two-shell model for the micelle form factor (core plus interfacial layer) and a screened Coulomb interactive potential for the interparticles potential. For both deuterated and hydrogenated surfactant, C222 ligand complexes the sodium micellar counterion and is mainly located at the interface partially screening the micelle surface charge. Counterion complexation produces, as compared to pure SDS micellar solutions, an increase of the interfacial layer thickness and a decrease of the micellar surface charge, of the contact potential, and of the average aggregation number. We report a detailed analysis of the micelle structure and intermicellar interaction potential.