Central-radial bi-porous nanocatalysts were synthesized by derivation from dendritic porous supports with hierarchical inorganic functional layers. The nanostructure exhibited a high unit loading capacity, accessible internal catalytic sites and protective mesoporous shell encapsulation. The nanocatalysts were utilized for efficient and stable heterogeneous catalytic reduction of 4-nitrophenol to 4-aminophenol with robust magnetic recyclability.