The possibility of the combination of electrolysis and subcritical water as a novel electrolyte was investigated. A stainless steel reactor was used as an undivided electrochemical cell containing platinum as the anode and a stainless steel reactor as the cathode. At first, the effect of temperature on the electrolysis current as the main parameter was studied in a cell containing only pure water and a supporting electrolyte. It was realized that the electrolysis current (and, consequently, the electrolysis efficiency) increased linearly with temperature because of the change in viscosity and other physicochemical properties of subcritical water. As a result, at 553 K the electrolysis efficiency was over 14-fold higher than that under ambient conditions. The possibility of the applicability of the above combined techniques for the decomposition of o-xylene was also followed as a model for benzene, toluene, ethylbenzene, and xylene (BTEX) compounds. The effect of experimental conditions such as the electrolysis duration, the electrolysis voltage, and the temperature of subcritical water was investigated. Several decomposed products were identified. o-Xylene was directly electro-oxidized to 2-methylbenzyl alcohol and consecutively to the other oxidation products. Also, hydroxide ions were oxidized to oxygen molecules, where hydrogen was generated on the cathodic surface. The final oxidation product of the electro-oxidation reaction was identified as carbon dioxide. The results indicate that more than 95% of o-xylene can be decomposed under optimum conditions.