In this work, a facile route using a simple solvothermal reaction to synthesize 3D porous flowerlike hierarchical nanostructures (HNs) of α-Fe(2)O(3) without employing templates or matrices for self-assembly is presented. The morphology and compositional characteristics of the 3D HNs were investigated by various techniques. The 3D HNs composed of 2D nanopetals, were intercrossed with each other and constructed from nanobricks with a length of about 100 nm and a diameter of about 30 nm. Influencing factors such as the reaction time, dosage of reactants and the solvents are systematically investigated. A possible formation mechanism for the 3D HNs is proposed. On the basis of characterization results, the growth of such 3D HNs has been proposed as a self-assembly followed by Ostwald ripening process. The specific surface area of the 3D HNs also was investigated by using nitrogen adsorption and desorption isotherms. The as-prepared α-Fe(2)O(3) HNs have a comparatively large Brunauer-Emmett-Teller (BET) surface area of about 52.51 m(2) g(-1). The photocatalytic properties of the as-obtained α-Fe(2)O(3) 3D HNs are systematically investigated, which was evaluated by the degradation of RhB dye under ultraviolet light irradiation. The result shows that photocatalytic activity is greatly affected by the hierarchical and porous structure.