The invention relates to a limestone-plaster wet method flue gas desulfurization composite synergistic agent, which comprises the following ingredients in percentage by mass: 40 percent to 50 percent of organic acid synergistic agents, 25 percent to 35 percent of organic salt synergistic agents, 15 percent to 20 percent of efficient activating agents, 5 to 10 percent of oxidation catalysts and 1 percent of tracers. The half dissolving time of limestone is shortened by more than 40 percent, and the dissolving speed of the limestone is greatly accelerated, so the activity of the limestone is greatly improved. Under the work condition of the designed surfur content, the circulation intensity of serous fluid can be reduced by one third to one half, the liquid-gas ratio of a system is reduced, the system resistance is reduced, the energy consumption of a desulphurization system is obviously reduced, the utilization rate of limestone and oxidation air is improved, and the scale formation and blockage effects on back-stage equipment are reduced. Under the condition that the coal-fired sulfur exceeds the design value, the utilization rate of the oxidation air can be improved by 50 percent to 60 percent, on the basis without transforming the original oxidative system, the oxidation effect that when the fired-coal surfur content exceeds 20 to 30 percent can be met, and the requirements of the desulfurization efficiency and the clean flue gas SO2 discharge concentration are met.