Although nanoparticles, nanorods, and nanosheets of α-Fe₂O₃ on graphene sheets have been synthesized, it remains a challenge to grow 3D α-Fe₂O₃ nanomaterials with more sophisticated compositions and structures on the graphene sheets. Herein, we demonstrate a facile solvothermal route under controlled conditions to successfully fabricate 3D α-Fe₂O₃ hollow meso–microspheres on the graphene sheets (α-Fe₂O₃/RGO HMM). Attributed to the combination of the catalytic features of α-Fe₂O₃ hollow meso–microspheres and the high conductivity of graphene, α-Fe₂O₃/RGO HMM exhibited promising electrocatalytic performance as a counter electrode in dye-sensitized solar cells (DSSCs). The DSSCs fabricated with α-Fe₂O₃ HMM displayed high power conversion efficiency of 7.28%, which is comparable with that of Pt (7.71%).