In-plane heterostructures exhibit extraordinary chemical and electron transfer properties, which have received remarkable research attention. However, the synthesis of an in-plane Mo2C/MoO3 heterostructure has been rarely reported, and the deep investigation of the effect of its fine structure on reactivity is of great significance. Notably, the in-plane heterostructures endow the material with abundant grain boundaries, which facilitate the formation of surface acid sites and active oxygen species, thus contributing to the sensing performance. Our work provides a promising platform to design in-plane heterostructures for various advanced applications.