The most reactive hydroxyl radical(·OH) was generated by electrochemical approach with safe water as the complete atom source. The direct evidence for ·OH formation was obtained by electron spin resonance method. The powerful ·OH electrochemically generated could effectively degrade organic pollutants and reduce the toxicity of wastewater. Electrochemical disinfection by ·OH was considerably efficient even without the aid of active chlorine. Bacteria inactivation of 99.99% was achieved for contact time of 30 min and current density of 5 mA.cm-2. In comparison with active chlorine, ·OH is rather attractive as a promising environmentally benign disinfectant and opens a new route for microbial inactivation.