Making full use of solar energy and achieving high charge separation efficiency are critical factors for the photocatalysis technique. In this work, we report core-shell structured fibrous phosphorus (f-P) coated P-doped Cr2O3 (Cr2O3:P@f-P) hybrid composites with a strong optical absorption in the full region of 200-2600 nm. The Cr2O3:P@f-P hybrid composites exhibit a record photocatalytic efficiency under UV, visible and near-infrared light irradiation, demonstrating as promising photocatalysts for the full utilization of solar energy. Systematical investigations combining experimental and theoretical work show that P doping modifies the electronic band structures and creates defective levels in the forbidden gap of Cr2O3 which extends the optical absorption to the visible and near-infrared regions. Highly crystalline fibrous phosphorus in situ grown on the Cr2O3 particles constructs a core-shell hybrid structure which guarantees intimate interfacial contact between f-P and Cr2O3:P and facilitates the separation of photogenerated electron-hole pairs. This study develops a promising system based on earth abundant element P to utilize the overall spectrum of sunlight for photochemical applications.