Ti/IrOx–TiO2/IrO2 and Ti/IrO2–Ta2O5 electrodes were prepared using thermal decomposition procedure, respectively. The microstructure and electrochemical properties of the electrodes were studied with scanning electron microscope (SEM), X-ray diffraction (XRD), potentiodynamic polarization and accelerated life test. Experimental results showed that the Ti/IrOx–TiO2/IrO2 electrode has better electrocatalytic activity for oxygen evolution and higher stability, compared with the Ti/IrO2–Ta2O5 electrode under the same conditions. The high electrocatalytic activity of Ti/IrOx–TiO2/IrO2 electrode could be correlated with a large number of IrO2 particles on coating surface. The Ti/IrOx–TiO2/IrO2 electrode exhibits a three times longer service life than that of Ti/IrO2–Ta2O5, its superior stability was attributed to the IrOx–TiO2 interlayer, which contributes to form a metastable solid solution between IrOx and thin titanium oxide layer on titanium substrate during calcination and the improvement of the bonding of IrO2 layer with the substrate.