Two-dimensional (2D) layered nanostructures are emerging fast due to their exceptional materials properties. While the importance of physical approaches (e.g., guest intercalation and exfoliation) of 2D layered nanomaterials has been recognized, an understanding of basic chemical reactions of these materials, especially in nanoscale regime, is obscure. Here, we show how chemical stimuli can influence the fate of reaction pathways of 2D layered nanocrystals. Depending on the chemical characteristics (Lewis acid (1O2) or base (H2O)) of external stimuli, TiS2nanocrystal is respectively transformed to either a TiO2 nanodisc through a “compositional metathesis” or a TiO2 toroid through multistage “edge-selective structural transformation” processes. These chemical reactions can serve as the new design concept for functional 2D layered nanostructures. For example, TiS2(disc)-TiO2(shell) nanocrystal constitutes a high performance type II heterojunction which not only a wide range solar energy coverage (∼80%) with near-infrared absorption edge, but also possesses enhanced electron transfer property.