HighlightsThe zeolitic imidazolate framework functionalized modified layered double hydroxide (ZIF-8@MLDH) composite membranes with superior structural stability and Li+permeability are prepared by selectively growing ZIF-8 nanoparticles in the framework defects of the MLDH membrane.The tailor-made ZIF-8@MLDH membrane has a large Li+permeability of up to 1.73 mol m-2h-1and a high Li+/Mg2+selectivity of 31.9, which exceed most of the current 2D lamellar membranes.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01101-w.