AbstractA novel three-dimensional (3D) α-Fe₂O₃/MoS₂ hierarchical nanoheterostructure is effectively synthesized via a facile hydrothermal method. The zero-dimensional (0D) Fe₂O₃ nanoparticles guide the growth of two-dimensional (2D) MoS₂ nanosheets and formed 3D flower-like structures, while MoS₂ facilitates the good dispersion of porous Fe₂O₃ with abundant oxygen vacancies. This charming 3D-structure with perfect match of non-equal dimension exhibits high recyclable photo-Fenton catalytic activity for Methyl orange pollutant and nice specific capacity in reusing as supercapacitor after catalysis. The synergistic effect between Fe₂O₃ and MoS₂, the intermediate nanointerfaces, the 3D porous structures, and the abundant oxygen vacancies both contribute to highly active catalysis, nice electrochemical performance and stable cycling. This strategy is simple, cheap, and feasible for maximizing the value of the materials, as well as eliminating the secondary pollution.