By calculating the electron structures of the phases that phosphor, sulfur and alloying elements dissolving in γ-Fe,the reason why alloying elements can bring centerline segregation in continuous casting slab (CCS) with nA, the number of electrons on the strongest covalent bonds, and the structure formation factor S were investigated, and an electron structural criterion to control and to eliminate the centerline segregation was advanced. Basing on this, the electron structures of a part of rare earth phosphides and sulfides are calculated, the physical mechanism that rare earth elements can control the segregation of phosphor and sulfur is analyzed, and the criterion is well verified.