Photo self-Fenton catalyst is a promising candidate for solar energy conversion and environmental remediation. Here we reported a Tungsten trioxide/carbon nitride (WO3/CN) in which the surficial amino groups on CN are inserted into the WO3 matrix, forming coordinate covalently Nδ− → Wδ+ in construction of an intimate S-scheme heterojunction. The intimantance promotes the transfer of photocarriers under light irradiation. The nanohybrids produced hydrogen peroxide (H2O2) in a rate about 20 times of pristine CN. A dual-path architecture in which H2O2 are produced via hole-water oxidation and electron-oxygen reduction was poposed. It is founded that ciprofloxacin also involved in production of H2O2 by their deprotonation to superoxide anions, and holes and hydroxyl radicals effectively attack the weak sites in skeleton of ciprofloxacin. This work suggests a great significance of strategy in self-producing of H2O2 in utilizing solar energy and molecular oxygen for water, particularly the surface water decontamination.