Hollow hierarchical Ni@C nanocomposites with highly dispersed Ni nanoparticles (NPs) embedded in well-graphitized carbon matrix have been synthesized by solid-state pyrolysis of simple, well-defined organic–inorganic layered nickel hydroxide. The integration of highly dispersed Ni NPs, high Ni NPs content (up to ∼88.01 wt%), well-graphitized carbon as well as strong Ni/carbon interaction in the Ni@C make them display excellent catalytic activity and stable magnetic recyclability toward the reduction of 4-nitrophenol by NaBH₄.