The invention provides a preparation method of an oxidation flocculation composite water treatment agent, which comprises the following concrete steps of weighing n-decyl alcohol, putting silver powder with the weight of 0.5-5.5% of n-decyl alcohol into a three-mouth flask, continuously supplying nitrogen, adding 20ml ethylene diamine tetraacetic acid, quickly performing temperature rise to 100-300 DEG C, cooling to a room temperature after reaction completion, adding 10g trinitrotoluene, heating to 40 DEG C, stirring for 30min, cooling to the room temperature, adding trimethylamine and chitosan to a solution, performing a thermostatic reaction for 5h, naturally cooling to the room temperature, adding 10g dimethyl ether, 10g humic acid and 10g polyacrylamide, loading into a sealed pressure vessel, performing a reaction for 2-4h at 1.0-2.0MPa and 150-250 DEG C, performing ultrasonic oscillation on the solution for 60-90min, and obtaining the oxidation flocculation composite water treatment agent. The oxidation flocculation composite water treatment agent prepared by the method has the advantages of less consumption, high reaction speed, good flocculation effect and the like.