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In this paper, the influence of valence electron structure parameters on the adiabatic shearing sensitivity has been studied for two grade steels (30CrMnMo and C45E4) as a function of covalent pair number and lattice electron number by empirical electron theory of solids and molecules in high‐speed penetration process. The research shows that the adiabatic shearing sensitivity increases with the increase of the covalent electron pair number nA, decreases with the increase of the lattice electron number nl. The nA of each structure unit in 30CrMnMo steel is larger than that in C45E4steel, the nl of each structure unit in 30CrMnMo steel is smaller than that in C45E4steel. Therefore, the adiabatic shearing sensitivity is higher for 30CrMnMo targets damaged by adiabatic shear failure, and yet C45E4 targets were damaged by ductile fracture without any adiabatic shear band. The basis can be provided for appropriately selecting and designing materials with different adiabatic shearing sensitivity by studying the specific alloy elements on the influence of adiabatic shearing sensitivity in valence electron structure level.