The steel solidification behavior in the mold during normal and breakout process is investigated on basis of microstructure observation from a bloom breakout shell about 500 mm in length. A total of three layers is observed in the breakout shell from the outer surface to the inner, namely, steady state layer, extra solidified layer, and adhesive layer. The steady state layer with equiaxed and columnar crystals is the true solidified shell under the normal casting condition. For the present bloom, the thickness of the steady state layer is about 10.96 mm at the location 500 mm below meniscus. The extra solidified layer forms in the breakout process where the liquid steel can solidify consecutively, and its thickness is about 1.59 mm on the breakout shell bottom. The boundary between extra solidified layer and steady state layer is a white band about 0.4 mm in thickness, where the solute elements C, Cr, and Mn are negative segregation. The adhesive layer is the attachment of the unsolidified steel in the inner face of the shell, in which the dendritic is quite smaller and the thickness is around 1.56 mm on the bottom of the breakout shell. Further insights are provided by a new mathematical model according to mass and energy conservation. The predicted thicknesses of steady state layer, extra solidified layer, and adhesive layer on the breakout bottom are 10.94, 1.69, and 1.57 mm, respectively. Favorable agreements are observed between the modeling results and the measurements.