The invention provides an Ag+-Fe2+ synergistic persulfate activating system and a method for degrading organic pollutants thereof. The synergistic activating system is composed of Ag+, Fe2+ and persulfate; the method for degrading the organic pollutants by means of the persulfate comprises the steps that 1, the Ag+-Fe2+ synergistic persulfate activating system is added into a to-be-treated compound aqueous solution and wastewater containing the organic pollutants, and a pH value of a reaction system is controlled to be 3-7; 2, at 15-50 DEG C, degradation treatment is conducted for 5-60 min. The Ag+-Fe2+ synergistic persulfate activating system forms a compound persulfate activation system, through Ag+-Fe2+ synergistic action, the purpose of activating the persulfate jointly is achieved, the reaction rate is improved, the degradation effect is improved, and advanced degradation of the pollutants is achieved.