AbstractTwo-dimensional metal dichalcogenide/monochalcogenide thin flakes have attracted much attention owing to their remarkable electronic and electrochemical properties; however, chemical instability limits their applications. Chemical vapor transport (CVT)-synthesized SnTiS₃ thin flakes exhibit misfit heterojunction structure and are highly stable in ambient conditions, offering a great opportunity to exploit the properties of two distinct constituent materials: semiconductor SnS and semi-metal TiS₂. We demonstrated that in addition to a metal-like electrical conductivity of 921 S/cm, the SnTiS₃ thin flakes exhibit a strong bandgap emission at 1.9 eV, owing to the weak van der Waals interaction within the misfit-layer stackings. Our work shows that the misfit heterojunction structure preserves the electronic properties and lattice vibrations of the individual constituent monolayers and thus holds the promise to bridge the bandgap and carrier mobility discrepancy between graphene and recently established 2D transition metal dichalcogenide materials. Moreover, we also present a way to identify the top layer of SnTiS₃ misfit compound layers and their related work function, which is essential for deployment of van der Waals misfit layers in future optoelectronic devices.