AbstractAt present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe₂, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of ‘design-and-build’ 2D layered heterojunctions for large-scale exploration and applications.