Alloying effects on the crystallization temperature and the crystallization process of Fe-Cr-C-B alloys were studied by DSC and X-ray diffractometer. The crystallization temperature linearly increased with increasing the concentration of Cr and metalloids. The activation energy for crystallization was in the range of 83-97 ㎉/㏖, and its dependence to composition was similar to that of the crystallization temperature. Three crystallization processes of primary, eutectic and polymorphic were occurred with alloy composition. The final stable crystalline phases were α-(Fe, Cr) (bcc), (Fe, Cr)₃B(orthorhombic) and (Fe, Cr),B (tetragonal) in Fe_(47)Cr_(35)B_(18) alloy, (Fe, Cr)₃(C, B) (orthorhombic) in Fe_(41)Cr_(35)C_(12)B_(12) alloy, and α-(Fe, Cr)(bcc) and (Fe, Cr)₃ (C, B) (orthorhombic) in all Fe-Cr-C-B alloys except Fe_(41)Cr_(35)C_(12)B_(12) alloy.