In this paper, environmental scanning electron microscopy (ESEM) is applied to characterizing the mineral and element distribution of chromite ore processing residue (COPR). The test results show that Cr-bearing brownmillerite occurs in the rim of COPR particle, while hydroandradite with Cr (Ⅵ) in its structure presents inside the COPR particle. Periclase and calcite occur in the interstitial area. Element analyses show that Ca, Fe and Al are distributed throughout the COPR particle, and Mg exists mostly in the interstitial area or on the particle surface. A lower content of Cr is evenly distributed in the COPR particle, while slightly higher concentration of Cr occurs inside the particle. It is suggested that it will take a relatively longer time for Cr to migrate out of COPR, especially fbr hexavalent chromium, so the leaching time and the particle size may be two important factors to affect the release of Cr (Ⅵ).