The invention discloses a chemical treatment method of heavy peracid emulsified and aged crude oil. The chemical treatment method comprises the following steps: preparing emulsion of heavy peracid emulsified and aged crude oil; adding a compound complex agent and a demulsifier into the emulsion, and carrying out thermal precipitation to realize the dehydration treatment of the heavy peracid emulsified and aged crude oil. The heavy peracid emulsified and aged crude oil refers to crude oil which is difficult to treat in the oil extraction and oil refining processes; the water content of emulsion is 15-60%. The treatment method of aged dirty oil has the advantages of being convenient in operation, simple in process, strong in applicability, low in cost, friendly to environment and the like. For the aged crude oil treated by the chemical treatment method disclosed by the invention, the water content is smaller than 1%, the normal external transportation standard and processing requirements of crude oil can be met, the safety and the potential safety hazard caused by the aged dirty oil can be obviously reduced, and the economical, environmental and social benefits are significant.