Complexation of thiazorylazododecylphenol (TADP) with Ni2+ at the surface of sodium dodecylsulfate, (SDS) micelles has been spectrophotometrically studied. Complicated spectral changes are analyzed by a factor and multivariate analysis, which implies the formation of [TDAP(OH-)Ni](0) as well as a simple 1: 1 complex of Ni2+ with TDAP at the micellar interface. All of the equilibrium constants required to describe this system are substantially affected by electrolyte concentrations. Coexistent electrolytes vary the surface potential of the micelle, and in turn influence the equilibria taking place on the micellar surface. The electrostatic potential estimated based on the equilibrium shifts is more negative than that calculated according to Poisson-Boltzmann, theory, which simply involves electrostatic effects. This disagreement is possibly caused by different aqueous environments around the micelle from bulk solution, which also facilitate the formation of unusual complex such as [TDAP(OH-)Ni](0). (C) 2003 Elsevier Inc. All rights reserved.