In this paper, we made the nano-TiO2/glass composite electrode through the sol-gel method by using tetrabutyl titanate and anhydrous alcohol as the raw materials and the ITO conductive glass as the carrier. With the help of the photoelectric catalytic effect of TiO2 and the strong oxidation of Na2S2O8 as well as the computer application technology, we decomposed rapidly of the organophosphorous compounds and detected the total phosphorous (TP) on-line accurately. And then we characterized the TiO2 particles by SEM and analyzed the factors which influenced the decomposition and detection of TP by this method. The results show that the optimum experimental conditions of this method should be as follow: the concentration of Na2S2O8 is 0.03mol/L, UV illuminating time is 10 min, electrode voltage is 8V and the pH value should be in the alkaline zone. At last, it is validated the method is reliable and accurate for the decomposition of the organophosphorous by the recovery experiments and the comparative experiments between this method and national standard method.