The invention provides a method of using a composite extracting agent for extraction and refining of phosphoric acid prepared through a wet process. The method successively comprises the procedures of pretreatment, extraction and refining and post-treatment, wherein in the procedure of pretreatment, the content of solid in extracted raw acid obtained after condensation, defluorination, sedimentation, decolouring and filtration is less than 0.05 wt%, in the procedure of extraction and refining, a composite extracting agent is used for countercurrent contact extraction and comprises ketone ether, alcohol and ester, the weight ratio of ketone ether to alcohol to ester is 60-80: 15-20: 5-15, the ketone ether comprises ketone and ether and the weight ratio of ketone to ether is 95-60: 5-40, and in the procedure of post-treatment, condensation, decolouring, desulphurization, condensation and filtration are carried out so as to obtain the product of 85% industrial phosphoric acid. The invention has the advantages of low requirements to extracted raw acid, low production cost, a good extraction effect and capability of producing more products of industrial phosphoric acid.