Ti-based anodes with a top layer RuO₂-TiO₂ oxides mixture and an inter-layer TiB₂ were prepared by two step processes, i.e. first the TiB₂ film was deposited on Ti-based anodes by means of magnetron sputtering and then the top layer RuO₂-TiO₂ oxides mixture was further deposited by a thermal decomposition process. The microstructure and phase constituent of the coatings were characterized by means of SEM and XRD, and the electrochemical properties of the anodes were evaluated by the polarization curves. The results show that the interlayer TiB₂ plays important role in suppressing the formation of the cross cracks of the RuO₂-TiO₂ layer and, facilitating the adhesion of the top layer to the substrate, therefore the RuO₂-TiO₂ and TiB₂ coated Ti-anodes exhibit better electrocatalytic properties rather than the only RuO₂-TiO₂ coated ones. In the meanwhile, the TiB₂ interlayer can suppress the occurrence of a TiO₂ film at the interface coating/substrate thus prolongs the life time of Ti-anodes. Besides, the inducing of the TiB₂ interlayer can reduce the potential of chlorine evolution, and thereby enhance the current efficiency of the Ti-anodes effectively.