This study reports the preparation of medium-thickness aluminum/steel composite plates with different diffusion layers using rheological cast-rolling technology. The thermodynamic software and first-principles were employed to determine the effects of different silicon contents on the solidification process and mechanical properties of the 6061 aluminum/steel composite plates. The research revealed that the Fe2Al5 phase on the steel side possessed a tongue-like preferential growth at a silicon content of less than 1.2 wt%. A granular Al–Fe–Si phase was formed on the aluminum side of the diffusion layer when the silicon content exceeded the saturation solubility (1.8 wt%), which completely suppressed the tongue-like preferential growth of the Fe2Al5 phase. First-principles calculations revealed that the matrixes showed superior toughness in comparison to binary intermetallic compounds (IMCs), while the toughness of binary IMCs surpassed that of ternary IMCs. The mechanical properties showed that the shear strength of the sample prepared by rheological cast-rolling was higher than that of composite casting and close to that of composite rolling, reaching a maximum value of 73.4 MPa. The shear strength initially increased and then decreased with an increase in isothermal diffusion time, and the fracture location was transferred from the loose FeAl3 to the Fe2Al5 phase. An increase in silicon content resulted in a slight increase in the microhardness of the diffusion layer, a delay of the peak value of the shear strength, and a reduction in the gradient of the shear strength. A substantial decrease in peak shear strength was observed when the silicon content reached 1.8 wt%.