The future bioeconomy depends on the increased utilization of renewable lignocellulosic resources from trees and other bioenergy crops. However, considering that the diffusion of ions, chemicals, and enzymes into secondary cell walls is critical to effectively utilize lignocellulosic biomass, the unidentified mechanisms underpinning this diffusion have hindered progress. Here, nanomechanical spectroscopy was used to measure changes in moisture-dependent relaxations of amorphous polysaccharides inside loblolly pine ( Pinus taeda) cell wall layers. The comparison with recent ion mobility measurements made in similar cell wall layers revealed that the mineral ion diffusion occurs via interconnecting nanoscale pathways of rubbery amorphous polysaccharides. This result contradicts previous assertions of cell wall transport being an aqueous process occurring through simple interconnecting water pathways. Because polymer diffusion and aqueous transport via water channels are such different phenomena, the identification of the diffusion mechanism in this manuscript opens up a new paradigm in lignocellulosic research. The utilization of lignocellulosic resources is expected to be accelerated because the extensive polymer science literature can now be used to design the molecular architecture of lignocellulosic biomass to optimize diffusion properties for specific uses, including biorefinery feedstocks, advanced materials, and wood-based construction materials.