Electrochemical degradation is a promising method for removing organic pollutants from water due to its low carbon footprint and high efficiency. In this study, we prepared Mn/carbon black-nickel foam electrodes using a co-precipitation method and characterized them using FESEM and X-ray photoelectron spectroscopy. We investigated the effects of applied voltage, plate spacing, electrolyte concentration, and initial norfloxacin concentration on the degradation of organic pollutants. The results indicated that Mn/carbon black-nickel foam electrodes exhibited excellent performance in promoting the generation of hydroxyl radicals (·OH) and enhancing the electro-Fenton effect. At optimal conditions, including an applied voltage of 6 V, plate spacing of 15 mm, electrolyte concentration of 20 mmol/L, and initial norfloxacin concentration of 10 mg/L, the norfloxacin removal percentage reached 83.9%. Additionally, the total organic carbon (TOC) removal percentage was 69.2%, and the energy consumption was 9.6 kW·h/m3. Furthermore, when compared to titanium ruthenium-nickel foam electrodes under the same conditions, the Mn/carbon black-nickel foam electrode exhibited a 15.8% increase in norfloxacin removal rate, a reduction of 0.6 kW·h/m3 in energy consumption, improved current efficiency, and significantly accelerated reaction rates. Overall, this study demonstrates the excellent catalytic effect of the Mn/carbon black-nickel foam electrode on the degradation of antibiotic pollutants.