Bioinspired fibrous materials have emerged as a unique class of matrix for fabrication of fiber-shaped nanomaterial assemblies. Here, we report a novel functional fiber-shaped nanohybrid for efficient removal of antimonite via in situ synthesis of ferric oxides anchored to silk nanofibril. The silk nanofibril matrix played important roles in the growth of ferric oxides via metal-ligand interactions. The achieved nanocomposites had high surface areas and activity with more functional groups, contributing to superior antimonite elimination. The nanocomposite achieved a maximum removal capacity of 159.9 mg/g toward antimonite. And the common interfering ions of SO, NO-, CO, PO and SiO exhibited negligible influence on antimonite removal. The mechanism study point that two factors are closely involved: surface complexation and hydrogen bonding. Benefiting from the low cost and environmental-friendly nature of silk fibroin as well as excellent removal capacity and high selectivity, it suggests that the nanohybrids might be promising for antimonite extraction from contaminated water.