The invention discloses a preparation method of carbon nano tube fiber-graphene composite material. The method comprises the following steps of: a, preparing carbon nano tube fiber, meanwhile, wetting and modifying the carbon nano tube fiber by solution; b, providing graphene, adding the graphene into water solution, forming uniformly dispersed graphene dispersion liquid under the action of ultrasonic wave; c, dropping a dispersing agent into the graphene dispersion liquid, and stirring uniformly; d, fully contacting the carbon nano tube fiber with the graphene dispersion liquid so as to coat the surface of the carbon nano tube fiber with the graphene; e, then, drying the carbon nano tube fiber coated with the graphene, thereby obtaining the composite material. The carbon nano tube fiber-graphene composite material provided by the invention keeps the mechanical property and the electrical property of the carbon nano tube fiber, and endows the surface of the carbon nano tube fiber with lots of functional modification groups, such as carboxyl, hydroxyl and epoxy group, so that the surface hydrophilicity of the carbon nano tube fiber can be regulated effectively.