Hierarchical flowerlike β-Ni(OH)(2) superstructures composed of intermeshed nanoflakes are synthesized by hydrothermal treatment with a mixed solution of C(2)H(4)(NH(2))(2), NaOH, and Ni(NO(3))(2). The as-prepared β-Ni(OH)(2) superstructures could be easily changed into NiO superstructures without great morphology change by calcination at 400 °C for 5 h. Furthermore, the TiO(2) nanoparticles can be homogeneously deposited on the surface of NiO superstructures by dispersing β-Ni(OH)(2) powders in Ti(OC(4)H(9))(4)-C(2)H(5)OH mixed solution and then vaporizing to remove the ethanol at 100 °C, and finally calcination at 400 °C for 5 h. The prepared NiO/TiO(2) p-n junction superstructures show much higher photocatalytic activity for photocatalytic degradation of p-chlorophenol aqueous solution than conventional TiO(2) powders and NiO superstructures prepared under the same experimental conditions. An obvious enhancement in the photocatalytic activity can be related to several factors, including formation of hierarchical porous structures, dispersion of TiO(2) particles on the surface of NiO superstructures, and production of a p-n junction. Further results show that NiO/TiO(2) composite superstructures can be more readily separated from the slurry system by filtration or sedimentation after photocatalytic reaction and re-used, compared with conventional powder photocatalysts. After many recycling experiments for the photodegradation of p-chlorophenol, the NiO/TiO(2) composite sample does not exhibit any great activity loss, confirming that NiO/TiO(2) sample is stable and not photocorroded.