Abstract2D layered materials, combined with ion intercalation and diffusion storage mechanisms, are among the most promising storage materials for high‐performance rechargeable ion batteries (especially NH4+ storage systems). However, slow interlayer ion diffusion dynamics hinder their development. Most of the research focuses on the diffusion mechanism of interlayer hydrogen bonds, ignoring the special structure and function of the interlayer. In this study, the Mg(H2O)62+ intercalation strategy of MoS2 is proposed and the weak interlayer constraint and sulfur vacancy interlayer structure are co‐constructed. It is found that the intercalation of ions increased the interlayer spacing, effectively increased the ion storage space, and reduced the interlayer constraint of NH4+; Meanwhile, sulfur vacancy reduces the activity and number of NH4+ coordination sites. This special interlayer structure promotes the diffusion kinetics of NH4+. This aspect of concern has been almost ignored in previous studies. This work advances to provide insights and a fundamental understanding of ion diffusion behavior in layered structural features, paving the way for the development of sustainable energy storage systems.