The evolution process of corner temperatures for a typical micro-alloyed steel S355 is numerically simulated under various working conditions. The microstructure near the corner cracks of the S355 slab is experimentally examined, and the austenite/ferrite transformation temperatures of S355 steel during heating and cooling are measured. The results indicate that the right-angle slab corner temperature at the exit of the mould rapidly decreased to below Ar3 under intensive cooling in the foot roller zone. The film-like ferrite began to precipitate along the austenite grain boundary at the slab corner. The transformation from ferrite to austenite cannot be fully realized because the corner temperature cannot be quickly returned to Ac3 or higher. The slab transverse corner cracks occur along the film-like ferrite during the bending process. The chamfered slab, which modifies the original right angle of the slab into the 30° chamfered angle with a chamfered length of 60 mm, can significantly weaken the heat transfer and cooling effect of the slab corner. The chamfered slab corner temperature always remained above Ar3 during the bending and straightening processes. Precipitation of the pro-eutectoid film-like ferrite along the grain boundary cannot occur during cooling for the chamfered slab. The chamfered slab can keep the corner temperature above Ar3 and effectively avoid the occurrence of transverse corner cracks caused by grain boundary embrittlement.