Various alpha-Fe2O3 micro/nanostructures referring to spherical-like, bowl-like, cubic, and discoid shapes have been fabricated by a facile hydrothermal method using sodium bicarbonate as surfactant and alkaline reagents, displaying superior Fenton catalytic performances for degradation of Rhodamine 6G. Because of abundant exposed crystal surfaces such as (110) and (104) on the surfaces of bowl-like alpha-Fe2O3, the rapid degradation rate of 90.0% in 5 min is observed under the dark condition as the adding amount of H2O2 limiting to 300 mu L. Significantly, the enhanced catalytic performances of bowl-like alpha-Fe2O3/Au catalysts under natural light condition have been investigated and carried out by in situ reduction of well-distributed Au nanoparticles with average sizes of 3-6 nm. Due to the appropriate phase structures and heterogenous interface properties, the highest photo-Fenton catalytic activity with the degradation rate of 90.0% in 2 min can be obtained for alpha-Fe2O3/Au-0.01 composites.