Smooth particle hydrodynamics (SPH) is often adopted to simulate the waveform interface, which has a crucial effect on the bonding quality in explosive welding (EXW). However, owing to the nature of the SPH method, it is difficult to evaluate the influence of the air medium and calculate detailed waveform structure. In this study, a Cu-Q235 steel EXW model containing air medium was established using a structured arbitrary Lagrangian-Eulerian (S-ALE) method. A full-size 2D model was first performed to acquire welding parameters, which were set to the initial conditions for the next oblique collision method. Subsequently, the experiment was conducted to verify the accuracy of the simulations. The results show that the S-ALE method can effectively predict the waveform and acquire the detailed process of the EXW. With the addition of an air medium, the calculated velocity and pressure of the shock wavefront were approximately 3300 m·s−1 and 15 MPa, respectively. Despite the limited effect of the gas shockwave on the overall waveform, the influence on the large-scale or thin plates cannot be ignored. Furthermore, the simulation indicates that the participation of the air during the wave formation led to the generation of the pore in the vortex zone. The proposed method could predict the waveform structure and optimize the manufacturing process of composite plates in the atmospheric EXW.