The Fenton reaction, which refers to the reaction between ferrous ions and hydrogen peroxide to produce the OH radical, has not been widely applied to the disinfection of microorganisms despite being economic and environmentally friendly. Cho et al. have previously proposed the neutral photo ferrioxalate system as a solution to the problems posed by the Fenton reaction in acidic conditions, but this system still requires an external hydrogen peroxide supply. In the present study, we developed a simple disinfection technology using the photo or solar ferrioxalate reaction without the need for an external hydrogen peroxide supply. E. coli was employed as the indicating microorganism. The study results demonstrated the effectiveness of the photo ferrioxalate system in inactivating E. coli without any external hydrogen peroxide supply, as long as dissolved oxygen is supplied. Furthermore, the solar ferrioxalate system achieved faster inactivation of E. coli than an artificial light source at similar irradiance.