• Mechanism of interfacial Si enrichment in hindering Fe-Zn alloying was studied. • Localized Si-enriched zone was found between the steel matrix and the Zn coating. • Si-enriched zone inhibited Zn diffusion while allowing limited Fe diffusion. • Shape of the Si-enriched region evolved with increasing annealing time. • Si-enriched regions formed dispersed particle shapes within coating middle. Retained austenite plays a significant role in third-generation advanced high-strength steels (AHSS 3. Gen.), renowned for their excellent combination of strength and ductility. Silicon (Si) is a key element in stabilizing retained austenite. However, it introduces challenges in galvannealing and welding processes in Zn-coated steels, such as inhibited Fe-Zn alloying and increased susceptibility to liquid metal embrittlement (LME). This study investigated the mechanism of Si enrichment at the Zn/steel interface and its role in suppressing Fe-Zn interdiffusion during annealing. Using advanced techniques such as high-resolution transmission electron microscopy and atomic probe tomography, and Thermo-Calc DICTRA simulations, we analyzed the diffusion behavior and microstructural evolution in Zn-coated steels with varying Si contents. Si, driven by its low solubility in liquid Zn and Fe-Zn intermetallic phases, accumulates at the interface, forming a Si-enriched region that significantly suppresses Zn diffusion while permitting limited Fe diffusion. Numerical simulations revealed that the Si-enriched layer forms via the drag effect of the Fe-Zn reaction line, progressively concentrating Si at the interface as Zn diffuses. As annealing progresses, the morphology of the Si-enriched region evolves from layered, cloud-like structures to droplets and elongated dendritic forms, driven by Zn penetration and Fe consumption. These findings provide novel insights into the role of Si enrichment in mitigating LME and optimizing the Zn-coated AHSS 3. Gen., paving the way for advancements in automotive material design.