Graphene-on-diamond (GOD) composite structure has been attracting considerable attention due to its unique features for all carbon sp3-sp2 electronic applications. Whereby the electrical properties of diamond surface can be purposely tailored and significantly altered through transformed graphene layers. In this work, GOD composite structures were prepared by nickel (Ni)-catalyzed high-temperature rapid annealing, and were analyzed by Raman, Hall effect measurement and Transmission electron microscopy (TEM). The results show that the difference in surface conductivity of GOD composite structure is mainly related to the number of transformed graphene layers, which is mainly affected by annealing temperature, annealing time and the thickness of nickel film. Hall measurement and TEM results demonstrate that when the transformed graphene grows graphite with a lot of Ni atoms embedded into diamond, the surface carriers of GOD composite structure are electrons. On the contrary, the surface carriers are holes while the transformed graphene contains about 3 or 5 layers. These findings may provide a route for GOD structure to become a strong candidate for next generation complementary diamond electronic devices.