The electrodes of IrO 2 –Ta 2 O 5 coated titanium were prepared using conventionally thermal decomposition procedure and polymer sol–gel (Pechini) method, respectively. The microstructure and electrochemical properties of the electrodes were studied with scanning electron microscope (SEM), energy dispersive X-ray (EDX), atomic force microscope (AFM), potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and accelerated life test. As compared with the electrode formed using the traditional method of thermal decomposition, the oxide electrode prepared by Pechini method presents morphology of higher nano-scale roughness and more uniform surface composition with little precipitates. It also has larger electrochemically active surface area, better electrocatalytic activity for oxygen evolution and higher stability.