The design of van der Waals (vdW) heterostructures by integrating distinct two-dimensional (2D) materials remains a central strategy for tailoring novel functionalities or enhancing intrinsic properties beyond those of their individual components. In this work, direct epitaxial Bi₂Te₃/MoS₂ vdW heterostructures are synthesized via a sequential chemical vapor transport (CVT) approach. By optimizing the growth parameters, it was observed that the deposition of Bi₂Te₃ crystals is highly substrate-dependent, with preferential nucleation occurring on MoS₂ rather than directly on the sapphire substrate. This selective nucleation may be related to the different surface diffusion characteristics of MoS₂ and sapphire. Compared with sapphire, the MoS₂ surface provides more favorable diffusion and nucleation conditions for Bi–Te species, promoting preferential lateral growth of Bi₂Te₃ on MoS₂. Furthermore, the lateral size and thickness of Bi₂Te₃ crystals vary over a broad range as a function of the growth conditions. These findings provide practical insights into parameter-controlled growth of Bi₂Te₃/MoS₂ vdW heterostructures using sequential CVT and highlight their potential for applications in electronic and optoelectronic devices.