Boron doped diamond (BDD) electrodes were activated in steam at various temperatures, resulting in high quality BDD electrodes with a porous microstructure. Distinct columnar structures were observed by scanning electron microscopy. The electrochemically active surface area of the steam-activated BDD was up to 20 times larger than the pristine BDD electrode owing to the porous texture. In addition, a widening of the potential window was observed after steam activation, suggesting that the quality of BDD was enhanced due to oxidative removal of graphitic impurities during the activation process.