This study synthesized boron-doped diamond (BDD) thin films using hot-filament chemical vapor deposition at different carbon-to-hydrogen (C/H) ratios in the range of 0.3–0.9%. The C/H ratio influence, a key parameter controlling the balance between diamond growth and hydrogen-assisted etching, was systematically investigated while maintaining other deposition parameters constant. Microstructural and electrochemical analysis revealed that increasing the C/H ratio from 0.3% to 0.7% led to a reduction in sp2-bonded carbon and enhanced the crystallinity of the diamond films. The improved conductivity under these conditions can be attributed to effective substitutional boron doping. Notably, the film deposited at a C/H ratio of 0.7% exhibited the highest electrical conductivity and the widest electrochemical potential window (2.88 V), thereby indicating excellent electrochemical stability. By contrast, at a C/H ratio of 0.9%, the excessively supplied carbon degraded the film quality and electrical and electrochemical performance, which was owing to the increased formation of sp² carbon. In addition, this led to an elevated background current and a narrowed potential window. These results reveal that precise control of the C/H ratio is critical for optimizing the BDD electrode performance. Therefore, a C/H ratio of 0.7% provides the most favorable conditions for applications in advanced oxidation processes.