Owing to the high toxicity of CrVI species to human health and the ecosystem, much attention has been paid to the development of efficient adsorbents for CrVI. Herein, MIL‐100(Fe) was successfully utilized as a precursor for the carbothermal reductive synthesis of nanoscale zero‐valent iron functionalized porous carbon (nZVI@C) for the effective removal of CrVI. The organic ligands in MIL‐100(Fe) were transformed into a porous carbon matrix, whereas the Fe–O clusters were reduced in situ to nZVI owing to the strong reducibility of pyrolytic carbon. Additionally, the nZVI was distributed uniformly in the carbon support with a high loading and controllable particle size. Highly toxic CrVI species were efficiently degraded into less toxic CrIII species at the nZVI reductive sites, and then the CrIII species precipitated as (CrxFe1–x)(OH)3 in the porous hybrids. The CrVI adsorption capacity of the developed nZVI@C reached 206 mg g–1 under optimal conditions. Furthermore, the excellent magnetic performance of nZVI@C makes it convenient for CrVI remediation through simple magnetic separation. These outstanding characteristics indicate the promising potential of the developed material as an adsorbent for the efficient removal of CrVI from industrial wastewater.