The catalytic activity of materials is highly dependent on their composition and surface structure, especially the density of low-coordinated surface atoms. In this work, we have prepared two-dimensional hexagonal FeS with high-energy (001) facets (FeS-HE-001) via a solution-phase chemical method. Nanosheets (NSs) with exposed high-energy planes usually possess better reaction activity, so FeS-HE-001 was used as a counter electrode (CE) material for dye-sensitized solar cells (DSSCs). FeS-HE-001 achieved an average power conversion efficiency (PCE) of 8.88% (with the PCE of champion cells being 9.10%), which was almost 1.15 times higher than that of the Pt-based DSSCs (7.73%) measured in parallel. Cyclic voltammetry and Tafel polarization measurements revealed the excellent electrocatalytic activities of FeS-HE-001 towards the I ₃^–/I^– redox reaction. This can be attributed to the promotion of photoelectron transfer, which was measured by electrochemical impedance spectroscopy and scanning Kelvin probe, and the strong I ₃^– adsorption and reduction activities, which were investigated using first-principles calculations. The presence of high-energy (001) facets in the NSs was an important factor for improving the catalytic reduction of I ₃^–. We believe that our method is a promising way for the design and synthesis of advanced CE materials for energy harvesting.