Chromium is one of the eight most popular inorganic soil pollutants in China, and its bioavailability is determined by the chemical states. Amendments, which are able to change the chemical forms of chromium and decrease its bioavailability, have received considerable attention in recent years. In this work, the formation of Cr-based layered double hydroxides (LDHs) and the immobilization of Cr in solution and soil were systemically investigated. The formation of Cr-based LDHs is strongly depended on the layer charges, aging temperatures and reaction time, as identified by X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray absorption fine structure (XAFS) spectrum. According to the pot experiment results, the concentration of Cr in the overground part of Brassica Chinensis L. was significantly decreased to 1.50–2.03 µg kg^− 1 in the present of amendments. In total, the finding of LDHs formation on amendments and the thermodynamic stability of LDHs provides a new insight into the remediation of Cr-polluted soils.