The rapid reduction of Cr(VI) across a wide pH range, from acidic to alkaline pH conditions to stable Cr(III) species for efficient remediation of Cr(VI) pollution, has long been a challenge. Herein, we propose a new concept of in situ nanoconfinement catalysis (iNCC) for highly efficient remediation of Cr(VI) by growing nanosheets of in situ layered double hydroxide (iLDH) on the surface of Al−Mg−Fe alloy achieving chemical reduction rates of >99% in 1 min from pH 3 to 11 for 100 mg L −1 Cr(VI) with a rate constant of 201 h −1 . In stark contrast, the reduction rate is less than 6% in 12 h with a rate constant of 0.77 h −1 for the pristine Al−Mg−Fe alloy. The ultrafast reduction of Cr(VI) is most likely attributed to the synergistic catalysis of Al 12 Mg 17 and Al 13 Fe 4 and nanoconfinement of MgAlFe-iLDH and superstable mineralization of Cr(III) by MgAlCr III -and MgFeCr III -iLDHs. This study demonstrates the potential of in situ nanoconfinement catalysis on redox transformation for environmental remediation.