The electrosynthesis of pentoxide dinitrogen from tetroxide dinitrogen with RuO₂-IrO₂ coatings on the Ti substrate as anode and IrO₂ coatings on the Ti substrate as cathode, and PTFE membrane as separator was carried out in a semi-continuous plate-and-frame electrolyzer at a constant voltage. Influences of technological parameters such as the initial concentration of tetroxide dinitrogen in anolyte solution, the flow rate of the anolyte and temperature on the electro-oxidation of tetroxide dinitrogen to form pentoxide dinitrogen were investigated. At an initial concentration of tetroxide dinitrogen in anolyte solution below 45% the current efficiency and specific energy improved with increasing the initial concentration of tetroxide dinitrogen in anolyte. At an initial concentration of tetroxide dinitrogen in anolyte solution above 45% the current efficiency tended to a constant value. However, there no significant change in the yield of pentoxide dinitrogen was found with increasing the initial concentration of tetroxide dinitrogen in anolyte solution. The higher the flow rate of the anolyte is, the higher the current efficiency and yield of pentoxide dinitrogen are and the lower the specific energy. There was an initial increase in both the current efficiency and yield of pentoxide dinitrogen with increasing temperature up to a maximum at 6 ℃, followed by a decrease in both the current efficiency and yield of pentoxide dinitrogen as temperature further increased. The tendency of the change in the specific energy was inverse with that both the current efficiency and yield of pentoxide dinitrogen. The optimized technological parameters for the electro-oxidation of tetroxide dinitrogen are initial concentration of tetroxide dinitrogen in anolyte solution of 45%, electrochemical reaction temperature of 6 ℃ and flow rate of the anolyte of 63 mL·min^-1.