Hexavalent chromium (Cr(VI)) is a pollutant with high migration ability, and the destiny of Cr(VI) is highly correlated with ferrihydrite (Fh). Montmorillonite (Mt) is a clay mineral abundantly presents in nature. Although Cr(VI) adsorption on montmorillonite or ferrihydrite has been studied, Cr(VI) behaviors during the Fh-Cr-Mt coprecipitates transformation still remain unknown. In this study, calcium montmorillonite (Ca-Mt) or sodium montmorillonite (Na-Mt) was coprecipitated with ferrihydrite and Cr(VI). Effect of Ca-Mt (or Na-Mt) incorporation on coprecipitates transformation and Cr(VI) behaviors during aging were investigated. The results showed that Ca-Mt or Na-Mt incorporation inhibited the transformation of ferrihydrite in Fh-Cr-Ca-Mt or Fh-Cr-Na-Mt at the initial pH of 5.0, 7.0 and 9.0. During aging, two kinds of Mt were supposed to interact with Fh to form the FeOSi and FeOAl bonds, and thus the formation of hematite and goethite were limited. By testing the Cr(VI) distribution in each phase of coprecipitates during transformation, delay on Cr(VI) migration and redistribution could be found in systems added with montmorillonite, and Cr(VI) was retained in coprecipitates to a greater extent compared with the systems without montmorillonite addition. The results of this study contribute to increasing our knowledge about the role of clay minerals on the coprecipitates transformation when they coexist at different pH values. It is also significant for the heavy metals polluted sites repairing.