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The counter electrode (CE) is an important and vital part of dye-sensitized solar cells (DSSCs). Pt CEs show high-performance in DSSCs using iodide-based electrolytes. However, the high cost of Pt CEs restricts their large-scale application in DSSCs and the development of Pt-free CE is expected. Here, α-Fe₂O₃/reduced graphene oxide (α-Fe₂O₃/RGO) composites are prepared as the Pt-free CE materials for DSSCs. A simple hydrothermal technique was used to disseminate the α-Fe₂O₃ solid nanoparticles uniformly throughout the RGO surface. The presence of the α-Fe₂O₃ nanoparticles increases the specific surface area of RGO and allows the composites to be porous, which improves the diffusion of liquid electrolyte into the CE material. Then, the electrocatalytic properties of CEs with α-Fe₂O₃/RGO, α-Fe₂O₃, RGO, and Pt materials are compared. The α-Fe₂O₃/RGO CE has a similar electrocatalytic performance to Pt CE, which is superior to those of the pure α-Fe₂O₃ and RGO CEs. After being fabricated as DSSCs, the current–voltage measurements reveal that the DSSC based on α-Fe₂O₃/RGO CE has a power conversion efficiency (PCE) of 6.12%, which is 88% that of Pt CE and much higher than that of pure α-Fe₂O₃ and pure RGO CEs. All the results show that this work describes a promising material for cost-effective, Pt-free CEs for DSSCs.