The invention provides a composite antichlor as well as a preparation and use method thereof. The composite antichlor comprises the following raw materials in parts by weight: 5-10 parts of sodium methylate, 25-35 parts of methanol, 5-10 parts of sodium hydroxide, 10-20 parts of sodium ethoxide, 10-15 parts of triethanolamine, 15-25 parts of phenylamine, 10-15 parts of triethylamine and 20-25 parts of diethylamine. The preparation method of the composite antichlor comprises the following steps: weighing raw materials, and stirring the raw materials in a reaction kettle, so as to obtain the composite antichlor. The use method of the composite antichlor comprises the following steps: putting a chlorine-containing material into the stirring reaction kettle with the composite antichlor, carrying out a reaction, and further carrying out separation. The composite antichlor provided by the invention is reasonable in formula, low in preparation cost, good in dechloridation effect, low in byproduct quantity, small in toxicity, not liable to volatilization, not liable to combusting and safe to use, chlorine in a C5 resin can be effectively desorbed, additional values of products can be increased, and later process operation can be facilitated.