In this work, we report the synthesis of Ni(OH)(2) nanoparticles in the presence of the micelles formed by sodium dodecylbenzene sulfonate and cetyltrimethylammonium bromide. Key aspects about the particle formation and stability were studied by means of "in situ" zeta-potential measurements during the formation and dissolution of the nanoparticles. It was found that the intense electrostatic interaction between the positively charged Ni(OH)(2) sheets and the negative DBS- micelles provides a remarkable colloidal and electrochemical stability, on the other hand, positively charged micelles presented weak interaction with Ni(OH)(2) . By this way, it is presented a comprehensive interpretation of the interaction of the surfactants during the formation and stability of Ni(OH)(2) nanoparticles based on the intense superficial electric charge of the nanoparticles and how the interfacial and electrochemical properties are affected by. Also, electrodes were modified by using Electrophoretic Deposition and properly characterized by Atomic Force Microscopy and cyclic voltammetry.