Understanding the microscopic mechanisms for the nucleation and growth of two-dimensional molybdenum diselenide (2D MoSe 2 ) via chemical vapor deposition (CVD) is crucial towards the precisely controlled growth of the 2D material. In this work, we employed a joint use of transmission electron microscopy and CVD, in which the 2D MoSe 2 were directly grown on a graphene membrane based on grids, that enables the microstructural characterization of as-grown MoSe 2 flakes. We further explore the role of hydrogen gas and find: in an argon ambient, the primary products are few-layer MoSe 2 flakes, along with MoO x nanoparticles; while with the introduction of H 2 , single-layer MoSe 2 became the dominant product during the CVD growth. Quantitative analysis of the effects of H 2 flow rate on the flake sizes, and areal coverage was also given. Nevertheless, we further illuminated the evolution of shap…