The growth of high-quality graphene is always a focused issue in the field of two-dimensional materials, and the growth of graphene on brand new substrates has received considerable attention from scholars especially. The research on the nucleation mechanism of graphene deposited on a polycrystalline diamond substrate is of significance in the large-scale preparation of graphene in practice. Here in this work, the direct growth without transfer process of graphene on a diamond substrate is used to obtain the high-quality graphene. The reactive molecular dynamics simulation technology is adopted to imitate the process of graphene deposition and growth on bi-crystal diamond assisted by nickel catalyzed at an atomic level. The effect of the bi-crystal diamond grain boundary on the dynamic behavior of graphene nucleation and growth process is studied. The results demonstrate that the grain boundary carbon atoms can be used as a supplementary carbon source to diffuse into the nickel free surface and participate in the nucleation and growth of graphene. Furthermore, the effect of temperature on the diffusion behavior of carbon atoms is explored, finding that high temperature facilitates the dissociation of atoms in the grain boundary. When the deposition temperature equals 1700 K, it is most conducive to the diffusion of grain boundary carbon atoms in the nickel lattice, which effectively enhances the nucleation density of graphene. Besides, the effect of the deposition carbon source flow rate on the surface quality of graphene is explored, finding that the high-quality graphene surface can be obtained by adopting a lower carbon deposit rate of 1 ps ^–1at 1700 K. In brief, the research results obtained not only provide an effective theoretical model and analysis of the mechanism for diamond grain boundary assisted graphene deposition and growth, but also reveal the regular pattern of influence of deposition temperature and deposition carbon source flow rate on the surface quality of synthesized graphene. The present study can lay a theoretical foundation for the fabrication and application of new functional graphene-polycrystalline diamond heterostructures in the fields of ultra-precision manufacturing and microelectronics.