The invention relates to desulfurizing agents for gaseous phase esulfurization, and discloses a composite chelated iron desulfurizing agent and a preparation method thereof. High valent soluble ferricsalt is added into deionized water to be kept stirred, atype A chelating agent and a type B chelating agent are sequentially added and to be kept stirred, a pH buffer agent is gradually added till the solid matters are completely dissolved, the pH buffer agent is added continuously till the pH value is adjusted to 8.0-13.5, and the mixed matters are continuously stirred and react for 4-8 hours, so that the composite chelated iron desulfurizing agent is obtained; the type A chelating agent is one or more of HEDTA, EGTA, DGA, 2-peracetic acid malonic acid, 2-peracetic acid isobutyric acid and sodium salt and potassium salt thereof, the type B chelating agent is one or more of sodium citrate, sulfosalicylic acid, sodium sulfosalicylate dihydrate, sodium gluconate, mannitol and oligose, the mole ratio of the type A chelating agent to the type B chelating agent is from (1:1)to (1:0.25), the mole ratio of the chelating agents to high valent water-soluble ferric salt is from (1:1)to (3:1), and the mass percentage of Fe in the desulfurizing agent is 1.0-6.0wt%. The composite chelated iron desulfurizing agent is high in saturated sulfur capacity and stability, and wide in pH application range.