The invention relates to an ozone combined photo-excited peroxide VOCs (volatile organic chemicals) purification system and method, and belongs to the field of atmospheric pollutant control. The purification system mainly comprises a dust collector, a cooler, a photochemical atomization bed reactor, a gas distribution nozzle, a circulating pump, a particulate matter filtering device, a charging tower, a spray pipeline, a main flue, a demister and a product post-processing system. VOCs from a discharging source are firstly pre-oxidized into organic intermediate by the ozone in a flue, ultraviolet light excites peroxide to generate sulfate radical and hydroxyl free radical, so that the VOCs and the organic intermediate generated by oxidization of the ozone are further oxidized, and final decomposition products are harmless CO2 and harmless H2O. The VOCs in flue gas can be efficiently removed, secondary pollution is avoided in the removing process, and the novel VOCs purification system has a wide application prospect.