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We succeed in the controllable synthesis,topotactic phase transformation and chemical exfoliation of highly crystallized layered hydroxides with various metallic compositions(Fe,Co,Ni,Zn,Al,etc.),by rationally designing the oxidation state as well as by modifying the coordination geometry of metal cations.These transition metal hydroxides,consisting ofredoxable host slabs(M2+(OH)2(=)M3+OOH(=)M4+O2)and large interlayer spacing for ionic accessibility,afford a high potential in utilizing as active electrode materials for Faradaic pseudocapacitors.