A dual oxidant photochemical system, consist of persulfate (PS) and ceric (Ce(IV)) ions named as UV/PS/Ce(IV), was designed and examined for degradation of an organic pollutant, i.e., direct red 16 (DR16) in aqueous media. Using a recycled batch photo-reactor, the influence of the operational factors such as the initial pH and the PS or/and Ce(IV) to the DR16 initial molar ratios (oxidants: DR16 IMRs) were studied. The PS: Ce(IV): DR16 IMR was set 50: 10: 1 concerning the environmentally allowable total sulfate concentration (TSC) of 600 mg/L in the aqueous media. Under the mild operational conditions, i.e., natural initial pH and ambient temperature of 25 degrees C, the degradation efficiency of 30 mg/L of the DR16 after about 5.88 min, reached 90% with the operating cost of 1.98 US$/m(3). Also, using the power law kinetic equation and artificial neural network (ANN) method, the photochemical process was simulated and modeled successfully. The relative importance order of the process operating factors were determined by the sensitivity analysis as: reaction time > Ce(IV): DR16 IMR > PS: DR16 IMR > initial pH.