The invention of graphene has opened a brand new world of 2D supplies with ample parts and numerous bonding modes which have robust covalent bond in airplane however weak interplay out of airplane. One of many many alluring options of two-dimensional supplies is that they are often exfoliated in liquids. This peculiarity makes them capable of be exfoliated into skinny nanosheets with few layers and even monolayer. Exfoliation endows nanosheets distinctive laterally prolonged topology, novel mechanical efficiency and extremely uncovered floor, which are perfect for catalysis that primarily happen on materials floor. As well as, the exfoliated nanosheets present unprecedented optical and electrical properties owing to the two-dimensional confinement of electrons. The distinctive digital construction and floor construction of layered supplies has attracted large analysis pursuits in catalysis and power conversion discipline. This evaluate firstly introduces the historical past the event of layered supplies and summarizes structural chemistry based mostly on connection modes of laminate and kinds of intercalation ions. Moreover, rational strategies have been elaborated to realize controllable exfoliation of layered supplies in numerous sorts, with emphasis on the exfoliation mechanism and software sphere of every technique. Furthermore, we mentioned the most recent analysis progress of layered supplies as electrocatalysts and electrocatalyst helps the appliance in power conversion, and spotlight the connection between catalytic efficiency and the layered construction revealed by theoretical and experimental outcomes. Lastly, ahead strategies and prospects for the appliance of 2D layered supplies within the discipline of electrocatalysis have been additionally proposed.