Photocatalytic water splitting over semiconductors without using of any electron sacrificial agents is essential to the conversion of solar energy into chemical energy. Herein, we report remarkable photocatalytic hydrogen production from pure water without the assistance of electron sacrificial agents by using P-doped ZZn(x)Cd(1-x)S with rich S vacancies (Z(n)xCd(1-x)S-P) as the photocatalyst. It is found that interstitial P doping in ZnxCd1-xS solid solutions with rich S vacancies can prolong the lifetime of charge carriers and enhance the generation and separation of photogenerated electrons-holes, resulting in a H-2 evolution rate of up to 419 mu mol h(-1) g(-1) which is 72 and 73 times higher than those of ZnS-P (5.8 mu mol h(-1) g(-1)) and CdS-P (56 mu mol h(-1) g(-1)), respectively. Furthermore, the introduction of biomass-derived compound 5-hydroxymethylfurfural (HMF) into this system further promotes the photocatalytic hydorgen evolution reaction and simultaneously obtains value-added HMF oxidation products.