Diffusion in plant cell wall is dependent on moisture levels. The diffusion of inorganic ions in plant cell wall measured from MD simulation increases with cell wall hydration, and agrees well with prior XFM experiments . Diffusion for all species, but particularly K + and Cu 2+ is observed to have a moisture-induced glass transition at 15% equilibrium moisture content in wood. Generally, cation diffusion within the cell wall is slower compared to anion diffusion, because of strong interactions between carboxylate groups on the hemicellulose and cation retard the free diffusion of positively charged permeants. Armed with this mechanism, it is possible to design and engineer pathways to alter the mechano-chemical properties of lignocellulosic biomass, catering to applications in sustainable, chemical, and biomedical engineering. The insights obtained from our molecular simulations provide key guidelines for future experimental and computational studies, where we anticipate extending this model to explore the effects of cell wall polymer heterogeneity and acetylation on the diffusivity and ionic conductivity in plant biomass at different hydration index.