The invention belongs to sewage treatment technology and belongs to an improvement of flocculating agent compositions, and in particular relates to a high-synergistic non-co-soluble composite phosphorus removal flocculating agent and an application method thereof. The high-synergistic non-co-soluble composite phosphorus removal flocculating agent is prepared from 10 to 30 units of mass of polyaluminum sulfate, 20 to 40 units of mass of iron salt, 5 to 10 units of mass of copper sulfate, 5 to 10 units of mass of magnesium thiosulfate, and 2 to 10 units of mass of polyquaternium. A preparation method of the flocculating agent comprises the following steps: Step 1, adding water into a reaction kettle; Step 2, adding the iron salt into the water and stirring until the iron salt is completely dissolved; Step 3, adding aluminum sulfate, copper sulfate and magnesium thiosulfate into the aqueous solution in which the iron salt is dissolved and stirring until the three are completely dissolved;and Step 4, adding polyquaternium into the aqueous solution in which the iron salt, aluminum sulfate, copper sulfate and magnesium thiosulfate are dissolved, and stirring uniformly. By adding the high-synergistic non-co-soluble composite phosphorus removal flocculating agent, the total phosphorus content of sewage can be reduced to 0.5mg / L or below to reach the first-class A standard requirementfor sewage discharge, and the treatment effect is obviously better.