Tin-based Babbitt alloy/steel bimetallic castings were prepared by compound casting with different coating surface modification treatment. The defects of modified coating surface are effectively controlled, while the unmodified interface has a considerable number of micropores. In consequence, the additional composite surface modifier greatly increased the integrity of the bimetal interface and led to a significant improvement of shear strength to ~55.61 MPa, in comparison to its counterpart with no surface modifier of ~7.04 MPa. Based on extensive experimental investigation and theoretical analysis, the role of coating surface modifiers in the interfacial strengthening was revealed. Meanwhile, the diffusion behavior of the bimetal interface connection was analyzed by first-principles calculations. These results will shed new light on the understanding of the liquid–solid connection of bimetallic composites and improve defect control at the interface.