Industrial wastewater containing both organic and inorganic pollutants is being generated all the time. Efficient materials are highly needed to purify the polluted water. Thus, a hierarchical structured alpha-Fe2O3 with excellent adsorptive property has been synthesized by using a facile hydrothermal method. It can be prepared in macroscopic quantity. The as-synthesized alpha-Fe2O3 with silkworm cocoon-like morphology shows high efficiency in adsorbing Congo red (CR), Methyl orange (MO) and Cr(VI). The removal efficiency of CR, MO and Cr(VI) can reach 99.2%, 83.9% and 100% under appropriate conditions. Besides, this alpha-Fe2O3 shows high adsorptive ability for mixed CR and Cr(VI) in aqueous solution and the final removal rates can reach 94.7% and 97.9%, respectively. The adsorption kinetics fits well with the pseudo-second-order kinetic model. The results indicate that the product may find potential application in purification of wastewater containing both organic and inorganic pollutants.