In this work, the boron doping concentration, sp(3)/sp(2) ratio, grain size and other microstructures of boron-doped diamond (BDD) were regulated by changing the ratio of reactant gases during the chemical vapor deposition (CVD) process. And the intrinsic correlation between the microstructure of BDD electrode, electrochemical performance and reactive organic wastewater degradation efficiency was discussed. The results show that the ratio of B2H6, CH4 and H-2 has a significant effect on the microstructures and electrochemical properties of BDD. It was found that the electrode obtained with gas flow ratio of B2H6/CH4/H-2 at 0.3:3:97 showed the best performance for degrading reactive orange X-GN dye.