In this work, zero-dimensional (0D) high crystalline PrFeO3 worm nanocrystals were loaded over a three-dimensional (3D) rectangular WO3 to construct a 0D/3D PFO/W Z-scheme heterojunction by an in situ ultrasonic synthetic process. This heterojunction exhibited excellent photocatalytic activities towards the degradation of organic pollutants such as rhodamine B (RhB), Methylene blue (MB), and tetracycline hydrochloride (TC) in the presence of small amounts of H2O2 under visible-light irradiation. For example, the k value of PFO/W + H2O2 was about 67, 107, 45, 27, 11 and 14 times higher than pure H2O2, PrFeO3, WO3, PFO/W nanocomposite, PrFeO3+ H2O2 and WO3+H2O2 respectively during the degradation of MB. The trapping experiments and ESR measurements identified that the generated ·OH, ·O2−, and h+ were the active species involved in the catalysis. Further, the ·OH radical could be continuously generated by Fe3+/Fe2+ and W6+/W5+ conversion and played the dominant role in the degradation of organic pollutants. The superior photocatalytic performance of the PFO/W + H2O2 system was derived from the synergistic effect of the Z-scheme heterostructure and dual photo-Fenton-like oxidation (Fe3+/Fe2+ and W6+/W5+). A possible mechanism was postulated based on the results obtained. In summary, this study provided new insights into synthesizing an effectively heterogeneous 0D/3D Z-scheme dual photo-Fenton-like catalyst for water clarification.