Two-dimensional (2D) Mo₂C, as a new member of transition metal carbides, has many intriguing properties and potential applications in superconductors and electronic devices. The thermal stability of 2D materials is essential for the performance of the related devices, especially the ones with a vertical heterostructure. However, rare reports have demonstrated the thermal stability of Mo₂C and the effects of thermal stability on its performance. Here, we propose a facile and controllable method to directly oxidize Mo₂C to MoO_x, forming a MoO_x/Mo₂C heterostructure. During the oxidization process, an in situ technique is employed to uncover the transformation and thermal stability of the Mo₂C. The chemical vapor deposition Mo₂C shows high structural stability below 550 °C in Ar or below 350 °C in O₂, which demonstrates the high thermal stability and antioxidation of the Mo₂C film. The metallic Mo₂C is gradually oxidized to semiconducting MoO_x as the temperature increases above 350 °C. The oxidization rate can be easily controlled by adjusting the oxidation temperature and time. Further, the obtained MoO_x/Mo₂C vertical hybrid structure shows obvious Schottky junction behaviors, strongly indicating the perfect interfacial contact between the component layers. This work offers a new strategy for the controllable fabrication of high-quality 2D heterostructures.