Heterostructures of metal chalcogenides have attracted immense attention due to their enhanced charge transport, synergistic optoelectronic and catalytic properties. While heterostructures of metal−sulfide or metal−selenide nanocrystals have been studied extensively, those of metal−telluride nanocrystals are less explored due to the lower abundance of tellurium. However, tellurium, a group VI element placed at the border between metals and nonmetals in the periodic table, has the ability to adopt multiple oxidation states, from positive to negative, and a strong proclivity toward anisotropic growth. These singularizes it from other chalcogenide semiconductors and also helps the design of nanostructures of tellurium using Te(0) and Te 2− as the initial precursors. Hence, understanding Te chemistry for nanostructure formation in solution is an essential research area that needs further exploration. Considering this, herein, the synthesis of metal−telluride heterostructures using various chemical routes has been elaborated. The chemistry of the formation of these materials using the direct-seeded approach, cation and anion exchange, and coupling with noble metals, among other methods, are detailed in this review. Furthermore, different device applications of the Te-based heterostructures are analyzed and their performances are summarized. Additionally, the chemical manipulation of tellurium chemistry to engineer complex nanoheterostructures and their possible applications are also proposed as future prospects.