This paper describes a novel solution-based chemical process to architect hollow spheres of β-Ni(OH) 2 with controllable sizes in submicrometer and micrometer regimes. In the synthesis, starting nickel salt (nitrate) is first converted to 6-coordinated nickel ion complex [Ni(EDA) 3] 2+ (bidentate ligand EDA = C 2H 4(NH 2) 2) to avoid rapid solid formation. Hollow and core - shell β-Ni(OH) 2 spheres can be obtained with this template-free approach under one-pot conditions. The β-Ni(OH) 2 spheres are constructed from petal-like nanobuilding units which in turn are formed from even smaller nanocrystallites. The obtained porous β-Ni(OH) 2 spheres have a large specific surface area and show a unimodal pore-size distribution. Several preparative parameters have been examined and optimized. In particular, the concentration of divalent nickel in the starting solutions plays an important role in controlling thickness of the petal-like β-Ni(OH) 2 flakes and diameter of spheres. The β-Ni(OH) 2 flakes self-assemble into final spherical products through a donut-like structural intermediate. Furthermore, the β-Ni(OH) 2 hollow spheres can be used as solid precursors to synthesize other nanostructured derivatives. In this work, phase pure inorganic nanostructures, carbon nanotube (CNT) - inorganic nanocomposites, and inorganic - inorganic nanocom-posites (e.g., NiO, Ni, NiO/Ni, Ni/β-Ni(OH) 2, CNTs/NiO, CNTs/Ni, Ni@CNTs, Fe(OH) 3/β-Ni(OH) 2, Co(OH) 2/β-Ni(OH) 2, and Mg(OH) 2/β-Ni(OH) 2) have been prepared via solid-state thermal decomposition, gas-phase reduction, solution-based reduction, surface oxidation, chemical vapor deposition, and liquid-phase deposition. A greater picture for general synthesis of Ni-containing nanomaterials is thus obtained. © 2009 American Chemical Society.