generally prepared by molecular beam epitaxy (MBE) or wet-chemical methods, have started attracting attention. [11][12][13][14][15][16] However, due to the limitation of their small lateral size, the electronic properties and applications of 2D copper chalcogenides have rarely been touched despite dimensionality plays a crucial role in determining their properties. For example, the quantum confinement effect in reduced dimensionalities is considered to be effective on enhancing the power factor of thermoelectric materials, thereby improving the thermoelectric performance. [17] Thus, a novel synthetic strategy to prepare 2D copper chalcogenides with nanometer thickness and regular structures is needed to be developed.In addition, the small migration barrier of Cu ions, originated from their relatively loose bonding in copper chalcogenides, would result in a low defect formation energy and ubiquitous Cu vacancies. [4,8,18] Considering that ions/defects motion is the basis for resistive switching (RS) devices and related information storage technologies, it is natural to expect a memristive behavior with small switching thresholds in copper chalcogenides, which is highly desired in memristor research since most of 2D memristors own a switching voltage larger than 1 V. [19][20][21][22][23][24] Memristor-based electronics are a mainstream effort to realize low-power artificial intelligence through their analog multiply-accumulate operations in non von Neumann architecture, [25][26][27] and also they can be a promising platform for mimicking the actual biological synaptic connectivity maps. [26] Recently, memristive switching behavior was observed in relatively thick copper sulfide films, and was attributed to the reversible migration of Cu vacancies, [28] an intrinsic nature of copper chalcogenides. As a contrast, the reported 2D memristors mostly require either active metal (such as Cu and Ag) electrodes [24,[29][30][31] or precise control of oxidation to produce extrinsic mobilizable ions/defects/grain boundaries, [23,[32][33][34] which obviously restricts their further applications in an open architecture such as fabricating 2D heterostructures.van der Waals (vdW) epitaxy, which is based on relatively weak vdW interactions between the epitaxial layers and growth substrates, has been proven to be effective in synthesizing 2D planar structures from both layered and nonlayered materials. [3,35,36] In this work, we demonstrate the controllable preparation of a series of 2D binary copper chalcogenideCopper chalcogenides represent a class of materials with unique crystal structures, high electrical conductivity, and earth abundance, and are recognized as promising candidates for next-generation green electronics. However, their 2D structures and the corresponding electronic properties have rarely been touched. Herein, a series of ultrathin copper chalcogenide nanosheets with thicknesses down to two unit cells are successfully synthesized, including layered Cu 2 Te, as well as nonlayered CuSe and Cu 9 S 5 , via van der Wa...