The impact of initial mold temperatures on the formation of macrosegregated zone during the solidification process of large size steel ingots was numerically investigated. Three initial mold temperatures, representing the most commonly encountered industrial conditions, were examined. The flows induced by pouring jet, the thermo-solutal convection, and the thermomechanical deformation of the phases were all taken into consideration. The results indicated that a higher mold temperature increased the macrosegregation intensity in the upper section of the casting, along the centerline and in the mid-radius solute-enriched bands. The increase was associated with the increased temperature gradient in the casting, the advance predominance of thermal convection, and the delayed solidification process.