The invention relates to a polyvinyl carbazole/graphene composite material and a synthetic method and an application thereof. The synthetic method comprises the following steps: firstly oxidizing natural graphite to obtain graphite oxide; grafting an initiative and reversible addition-fragmentation chain transferred and polymeric group on the surface of the graphite oxide; and finally initiating a polymerization reaction of the N-vinyl carbazole on the surface of the graphite oxide by virtue of an initiating group to obtain the polyvinyl carbazole/graphene composite material via different reducing agents. The invention has remarkable characteristics as follows: the condition for initiating reversible addition-fragmentation chain transfer and polymerization on the surface is simple, the operation is easy, the polyvinyl carbazole can be firmly combined on the surface of the graphene by a covalent bond, controllable synthesis of macromolecular weight and molecular weight distribution can be achieved, the compatibility of the two materials can be effectively improved to a certain degree, and the current carrier transmission performance of the composite material is improved, thus having better application prospect and better economic benefits in the photoelectric information material field.