Pyrite nanomaterials show an excellent performance in remediating Cr(VI) contaminated wastewater. However, the high surface reactivity makes them easy to agglomerate to reduce their removal efficiency for Cr(VI). In this study, a novel hexapod-like pyrite nanosheet clusters material was successfully synthesized via a facile hydrothermal method with the assistance of fluorides. The products were pyrite microspherulites without fluoride ion. The hexapod-like pyrite nanosheet clusters had dramatically higher Cr(VI) removal efficiencies than microspherulites due to more dissolved Fe(II) and S(-II) into the suspension released for nanosheet clusters should be responsible for the enhanced removal rate of Cr(VI). The XPS analysis revealed that the rapid adsorption on the surface of pyrite nanosheet clusters followed by reduction of Cr(VI) to Cr(III) by FeS2 and subsequent precipitation of Cr(III) hydroxides/oxyhydroxides are responsible for the high removal capacity of Cr(VI). The hexapod-like pyrite nanosheet clusters material had high stability and longevity, and did not aggregate during the Cr(VI) removal process. The removal efficiency of Cr(VI) was still 100% after 5 cycles. Our study shows that the hexapod-like pyrite nanosheet clusters material could be acted as a recyclable and promising mineral material with high activity, stability, feasibility for remediating Cr(VI) contaminated environment.