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Different cooling process, annealing temperature and addition of B2O3 were experimented on the CaO-MgO-SiO2-Al2O3-Cr2O3-Fe2O3 slag system with an aim to investigate the chromium precipitation behaviour. The solidified slags were characterized by XRD, SEM, EDX and EPMA. It was shown that, under melt-quenching process, chromium was immobilized in amorphous structure in the slag with basicity lower than 1.0 and Cr2O3 content less than 4.0 wt%. It was also found that addition of B2O3 and higher annealing temperature would be helpful for the precipitation of chromium into spinel solid solution in slag with basicity of 1.5.