The invention discloses a graphene composite material, and a preparation method and an application thereof as a positive electrode material. The graphene composite material is formed by compositing graphene with 1,6,7,12,13,18-hexaazatrinaphthylene, wherein the mass of graphene accounts for 10%-30% of the total mass of the graphene composite material. The preparation method of the graphene composite material comprises a graphene and 1,6,7,12,13,18-hexaazatrinaphthylene obtaining step and a ball milling and mixing step. The graphene composite material has higher capacity; and because 1,6,7,12,13,18-hexaazatrinaphthylene has a large molecular system, the graphene composite material is not easy to dissolve in an electrolyte solution in a process of charge and discharge, so as to increase the positive electrode life. The preparation method has the advantages of simple process and easily controlled production conditions, effectively reduces the production cost, improves the production efficiency, and is suitable for industrialized production.