Flax straw biochar (FSBC)-supported nanoscale zero-valent iron (nZVI) composite (nZVI-FSBC) combining the advantages of nZVI and biochar was synthesized and tested for Cr(VI) removal efficiency from aqueous solution. Surface morphology and structure of FSBC and nZVI-FSBC were characterized by scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller techniques, which help to clarify the mechanism of Cr(VI) removal from aqueous solution. The adsorption of Cr(VI) onto FSBC and nZVI-FSBC was best described by the pseudo-second-order and the Sips model. Compared with FSBC, nZVI-FSBC remarkably improved the performance in removing Cr(VI) under identical experimental conditions. Due to the collaborative effect of adsorption and reduction of nZVI-FSBC, the adsorption capacity of nZVI-FSBC for Cr(VI) is up to 186.99 mg/g. The results obtained by XPS, XRD, and FTIR confirmed that adsorption and reduction dominated the processes of Cr(VI) removal by nZVI-FSBC. As a supporter, FSBC not only improved the dispersion of nZVI, but also undertook the adsorption task of Cr(VI) removal. The surface oxygen-containing functional groups of nZVI-FSBC mainly participated in the adsorption part, and the nZVI promoted the Cr(VI) removal through the redox reactions. These observations indicated that the nZVI-FSBC can be considered as potential adsorbents to remove Cr(VI) for environment remediation.