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Imparting surface coatings with conductivity is an effective way to prevent fire and explosion caused by electrostatic discharge. TiO 2 is a commonly used paint; however, intrinsic TiO 2 has poor electrical conductivity. Herein, we develop a method to make TiO 2 coating highly conductive by doping Ca 2+ into the TiO 2 lattice based on the introduction of graphene. It is demonstrated that doping Ca 2+ increases the carrier density of TiO 2 and its morphology changes from a sphere to a spindle shape, which increases the interfacial contact area between TiO 2 and graphene. Therefore, resistivity can be greatly decreased due to the construction of fast charge transport pathways from TiO 2 to graphene, resulting from an increase in the speed of interfacial charge transfer. In addition, the electronic properties of the samples are also studied through first-principles calculations before and after Ca 2+ doping. The result of the theoretical analysis is in agreement with that of experiments. Thus, the lowest resistivity of Ca 2+ -TiO 2 /graphene can reach 0.004 Ω cm. Consequently, the feature of superior conductivity of the Ca 2+ -TiO 2 /graphene composite endows it with practical application potential in the field of antistatic coating.