Transition metal dichalcogenides (TMDCs) are a type of two-dimensional (2D) layered materials connected by van der Waals forces, laying the foundation for the flexible construction of van der Waals heterostructures (vdWHs). Nevertheless, the main strategies for obtaining vdWHs, such as mechanical exfoliation or co-evaporation, still suffer from small size or non-uniform distribution. This work fabricated the vertically stacked PdSe2/PtSe2 heterostructures via one-step selenization of patterned metal seed layers. And the composition of different heterostructures was experimentally analyzed to determine the optimal selenization conditions for PdSe2/PtSe2 heterostructures. Furthermore, the energy band alignment at the PdSe2/PtSe2 interface was evaluated based on optical absorption spectroscopy (UV–vis) and ultraviolet emission spectroscopy (UPS) analysis. These vertically stacked vdWHs have attracted increasing attention in nano-electronic devices.