This study reports the first successful epitaxial growth of two-dimensional (2D) stanene on Bi₂Te₃(111) substrates using molecular beam epitaxy (MBE). The atomic and electronic structures of the stanene were determined through scanning tunneling microscopy (STM) and angle-resolved photoemission spectroscopy (ARPES), combined with first-principles calculations. The results confirm that stanene forms a biatomic-layer structure with a buckling height of approximately 0.1 nm. The electronic structure of stanene on Bi₂Te₃ was analyzed using ARPES, revealing two hole bands near the Γ point, which are attributed to stanene. The Fermi level is pinned by the bulk conduction bands of Bi₂Te₃, and the electronic structure shows a significant influence of the substrate, leading to band splitting and a small band gap at the K point. The study also demonstrates that the electronic properties of stanene can be tuned by chemical functionalization, such as saturating the p_z orbitals, which can induce quantum spin Hall (QSH) and quantum anomalous Hall (QAH) states. The results provide a foundation for further experimental studies and potential applications of stanene in future technologies. The weak coupling between stanene and the Bi₂Te₃ substrate is supported by the lack of chemical bonding and the similarity in electronic properties between the two materials. The study highlights the importance of the substrate in determining the electronic properties of stanene and opens new avenues for the exploration of stanene-based materials.This study reports the first successful epitaxial growth of two-dimensional (2D) stanene on Bi₂Te₃(111) substrates using molecular beam epitaxy (MBE). The atomic and electronic structures of the stanene were determined through scanning tunneling microscopy (STM) and angle-resolved photoemission spectroscopy (ARPES), combined with first-principles calculations. The results confirm that stanene forms a biatomic-layer structure with a buckling height of approximately 0.1 nm. The electronic structure of stanene on Bi₂Te₃ was analyzed using ARPES, revealing two hole bands near the Γ point, which are attributed to stanene. The Fermi level is pinned by the bulk conduction bands of Bi₂Te₃, and the electronic structure shows a significant influence of the substrate, leading to band splitting and a small band gap at the K point. The study also demonstrates that the electronic properties of stanene can be tuned by chemical functionalization, such as saturating the p_z orbitals, which can induce quantum spin Hall (QSH) and quantum anomalous Hall (QAH) states. The results provide a foundation for further experimental studies and potential applications of stanene in future technologies. The weak coupling between stanene and the Bi₂Te₃ substrate is supported by the lack of chemical bonding and the similarity in electronic properties between the two materials. The study highlights the importance of the substrate in determining the electronic properties of stanene and opens new avenues for the exploration of stanene-based materials.