The article discusses the conversion of glycerol to formic acid, a valuable chemical, through electrochemical methods. The challenges in this conversion process include complex reaction pathways and the need to enhance C-C bond cleavage for improved selectivity of formic acid. Traditional electrochemical methods in alkaline conditions yield formate, while acidic conditions face catalyst deactivation and slow kinetics. The article explores a photoelectrochemical method using a surface-fluorinated BiVO4 photoanode with a dual hydrogen-bond structure (BVO-F) to overcome these limitations. By forming dynamic double hydrogen bonds with water on the photoanode surface, the production of hydroxyl radicals is accelerated, facilitating C-C bond cleavage and enhancing formic acid production. The incorporation of hydrogen bond acceptors improves semiconductor adsorption properties, promoting desired oxidation pathways. Experimental measurements and theoretical calculations support these findings. The study achieved 79% formic acid selectivity and a solar-to-hydrogen conversion efficiency of 5.8% using a self-powered photoelectrochemical-photovoltaic tandem device. The structural characterization of the BVO-F photoanode revealed selective etching of the BVO (112) plane, amorphous layer formation with homogeneous dispersion of fluorine, and improved lattice spacing. The innovative approach of harnessing dual hydrogen bonds on the photoanode demonstrates potential in advancing glycerol-to-formic acid conversion and overall efficiency in the chemical industry.