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The effects of boron concentration and deposition pressure on the microstructure and electrochemical oxidation performance of Ti/BDD electrodes during HFCVD growth were systematically investigated. The electrode's surface morphology, composition, and electrochemical performance were characterized by scanning electron microscope (SEM), Raman spectroscopy, ultraviolet spectrophotometry, and an electrochemical workstation. Tetracycline served as a simulated pollutant to evaluate the electrochemical oxidation degradation performance of BDD electrodes fabricated with different boron concentrations and deposition pressures. As air pressure increases, the grain quality of the diamond gradually decreases, yet boron atom doping enhances the grain quality of the diamond. Under high boron concentration and low pressure conditions, the boron atom concentration on the diamond film's surface is elevated. BDD electrodes with larger grain sizes and higher boron atom concentrations, prepared under these conditions, exhibit superior electrochemical performance, increased degradation efficiency, and reduced degradation energy consumption.