Semiconducting carbon nitride materials were successfully prepared via a thermal poly-condensation of dicyandiamide as a precursor at >500 °C. The resulting materials were investigated as metal-free catalysts for the activation of H2O2 with visible light under mild conditions, using the decomposition of Rhodamine B (RhB) in aqueous solution as a model reaction. Results revealed that carbon nitride catalysts can activate H2O2 to generate reactive oxy-radicals under visible light irradiation without employment of any metal additives, leading to the mineralization of the dye. Factors affecting the degradation of organic compounds are pH values and the concentration of H2O2. Recycling of the catalyst indicated no obvious deactivation during the entire catalytic reaction, indicating good (photo)chemical stability of metal-free polymeric carbon nitride photocatalysts for environmental purification. This study demonstrated a promising approach for the activation of green oxidant, hydrogen peroxide, by the newly-developed polymer photocatalysts for environmental remediation and oxidation catalysis.