The direct growth of Sb₂Te₃ on graphene is achieved by atomic layer deposition (ALD) with pre-(Me₃Si)₂Te treatment. The results of atomic force microscopy (AFM) indicate Volmer–Weber island growth is the dominant growth mode for ALD Sb₂Te₃ growth on graphene. High resolution transmission electron microscopy (HRTEM) analysis reveals perfect crystal structures of Sb₂Te₃ on graphene and no interface layer generation. The characterization of X-ray photoelectron spectroscopy (XPS) implies the impermeability of graphene can maintain Sb₂Te₃ intact and isolate the adverse effects of substrates. Our study provides a step forward to grow high quality Sb₂Te₃ at low temperature and expand the potential applications of graphene in ALD techniques.