Ru-Ti-Ir-Ta/Ti quarternary metal oxide titanium anodes with sandwich coating structure were prepared by thermal decomposition and sol-gel method, respectively. The phases and micro-morphologies of the two coatings were investigated by means of XRD and SEM. The electrocatalytic activity of the coatings was studied and compared by Tafel curve and cyclic voltammetry curve. It is demonstrated that the main phases in the coatings prepared by different techniques are mainly rutile-type solid solution (Ir, Ta)O2 and (Ti, Ru)O2. Metallic Ru is found in the coating prepared by thermal decomposition. The crystals in the coating prepared by sol-gel are finer. The morphologies of the coatings by thermal decomposition and sol-gel are obviously different. The former is distinctly dry cracked-mud like, and the latter shows the detritus-type. The result indicates that the titanium anode prepared by sol-gel have the better electrocatalytic activity and corrosion resistance than that by thermal decomposition.