The effects of a sodium dodecyl sulfate, SDS, micellar solution on the coupling rates of two arenediazonium ions, ArN2+, with the hydrophobic 1-naphthylamine, 1NA and N-(1-naphthyl) ethylenediamine, NED, coupling agents and with the hydrophilic Na salt of 2-naphthol-6-sulfonic acid, 2N6S, have been studied. First, we explored the micellar effects on the thermal decomposition of the arenediazonium ions. The observed rate constants are slightly depressed or increased, depending on the nature of ArN2+, compared to those in pure water upon increasing [SDS]. Estimations of the corresponding association constant to the micelle indicate that a significant fraction of the arenediazonium ions are incorporated into the micelles even at low surfactant concentrations. The sulfonate group in 2N6S prevents its incorporation into the micellar aggregate due to the electrostatic barrier imposed by the micelles and, in consequence, the coupling reaction is inhibited. In contrast, when employing the naphthylamine derivatives, the observed rate constant increase rapidly up to a maximum at [SDS] less than or equal to 0.01 M and then decreases smoothly due to the dilution effect exerted by the micelles. The results are discussed in terms of the distribution of reactants between the micellar and aqueous pseudophases, the micellar-induced shift in the pK(a) of the amines, and the concentration/ dilution effect exerted by the micelles.