In this study, we investigated the relationship between the decarburization effect of the solid-state decarburization method for preparing silicon steel and the atomic diffusion behavior in the matrix, focusing on 1 mm thick Fe-0.18 wt% C-Si (1.5, 3.5 wt%) alloy strips as the research object. Solid-state decarburization experiments were carried out in an Ar-H2O-H2 atmosphere, and the self-diffusion behavior of C and Si in Fe-C-Si alloy system was simulated by molecular dynamics. The results show that the molecular dynamics simulation results are consistent with the decarburization experimental results. When the temperature is lower than 800 °C, the atoms maintain a compact bcc structure, so the migration rate of carbon is low. When the temperature rises, the atoms move violently, resulting in the destruction of the crystal structure. Because the atomic arrangement tends towards a disordered structure, the migration rate of C is high and the diffusion coefficient increases. The experimental results showed that the decarburization rate was accelerated. At the same temperature, the diffusion activation energy Q = 48.7 kJ·mol−1 of carbon in an Fe-3.5 wt% Si-C alloy matrix can be calculated. The diffusion activation energy of carbon Q = 47.3 kJ·mol−1 was calculated using a molecular dynamics simulation. When the content of Si is 3.5 wt% and 1.5 wt%, the diffusion series of Si can be expressed as D3.5Si, Si = 8.54 × 10−10 exp(−33,089.7/RT) m2/s and D1.5Si, Si = 2.06 × 10−9 exp(−46,641.5/RT) m2/s, respectively. When the Si content is 3.5 wt%, the diffusion coefficient of Si is larger. After diffusion to the near surface, it combines with the remaining O to form a continuous strip of SiO2. When the Si content is 1.5 wt%, the diffusion coefficient of Si is small. The remaining O diffuses in the matrix and will oxidize when encountering Si; it cannot aggregate in a highly-dispersed distribution. The lattice transition from face centered cubic lattice austenite to body centered cubic lattice ferrite occurred in the matrix of the thin strip. The diffusion coefficient of C in ferrite is much larger than that in austenite. Therefore, the decarburization rate suddenly increases before decarburization stagnation. With the increase in Si content, the diffusion activation energy of C decreases, which promotes the decarburization effect.