The invention provides a preparation method and application of a graphene/carbon nano-tube composite. The preparation method comprises the following steps: oxidizing graphene powder and a multiwalled carbon nano-tube together to obtain graphene oxide and an oxidized carbon nano-tube; carrying out ultrasonic peeling and dispersion on the graphene oxide and the oxidized carbon nano-tube; carrying out modification connection and reduction on the graphene oxide and the oxidized carbon nano-tube with ammonia water and ethylenediamine; and filtering, washing and drying a product after reaction to obtain the graphene/carbon nano-tube composite. The preparation method is simple and convenient, and reaction conditions are mild; in the preparation method, the graphene is connected with the carbon nano-tube through covalent modification, and the carbon nano-tube is connected between graphene slice layers. The graphene/carbon nano-tube composite prepared by the method has a fluffy and porous three-dimensional skeleton structure, and can be used for extracting and detecting melamine, clenbuterol, sulfadimidine sodium, indoleacetic acid, bambuterol, clorprenaline, dicofol, 2,2-bis(4-chlorophenyl)-1,1-dichloroethane or chlorofluoro thiochromanone.