Two-dimensional transition metal dichalcogenides (2D-TMDs) possess appropriate bandgaps and interact via van der Waals (vdW) forces between layers, effectively overcoming lattice compatibility challenges inherent in traditional heterojunctions. This property facilitates the creation of heterojunctions with customizable bandgap alignments. However, the prevailing method for creating heterojunctions with 2D-TMDs relies on the low-efficiency technique of mechanical exfoliation. Sb₂Te₃, recognized as a notable p-type semiconductor, emerges as a versatile component for constructing diverse vertical p–n heterostructures with 2D-TMDs. This study presents the successful large-scale deposition of 2D Sb₂Te₃ onto inert mica substrates, providing valuable insights into the integration of Sb₂Te₃ with 2D-TMDs to form heterostructures. Building upon this initial advancement, a precise epitaxial growth method for Sb₂Te₃ on pre-existing WS₂ surfaces on SiO₂/Si substrates is achieved through a two-step chemical vapor deposition process, resulting in the formation of Sb₂Te₃/WS₂ heterojunctions. Finally, the development of 2D Sb₂Te₃/WS₂ optoelectronic devices is accomplished, showing rapid response times, with a rise/decay time of 305 μs/503 μs, respectively.