This paper reports the development of a novel photoelectrochemical (PEC) oxidation technique based on UV-C irradiation and boron-doped diamond (BDD) anode and its application for the effective removal of the commercial herbicide halosulfuron-methyl (HSM). The study evaluated the influence of the following key operating variables in the photoelectrochemical process: current density, pH, temperature, and initial HSM concentration. With regard to HSM degradation/mineralization, the application of high current densities was found to be more advantageous once it promoted a more rapid degradation and mineralization, with 96% of total organic carbon removal, though the process became more energy-demanding over time. The initial concentration of HSM did not modify the relative degradation rate, though the degradation process became more efficient as expected in a mass-transfer controlled process. The use of acidic pH (pH 3) was found to be more suitable than neutral conditions; this is probably because an anionic resonant form of HSM may be formed in neutral conditions. The temperature level was also found to affect the rate of HSM removal and the degradation efficiency. Finally, the substitution of Na2SO4 by NaCl promoted a more rapid and effective degradation; this is attributed to high production of powerful oxidants. However, only 70% mineralization was reached after 3 h of treatment; this is probably related to the formation of recalcitrant chlorinated sub-products.