Adsorbed polyphenolic compound (resveratrol) to a wheat straw matrix was considered as a model system for studying the influence of particle sizes and crystallinity of cell wall cellulose on the extraction process from the matrix of plant material. The morphology of wheat straw particles was studied by scanning electron microscopy and changes in the crystal structure of cellulose were determined using X-ray diffraction. The kinetics of resveratrol extraction were studied using high-performance liquid chromatography (HPLC). The diffusion constants were determined for particles of different sizes and particles having the same size but varying in the degree of disordering of cellulose, the main component of cell walls. The applicability of the Axelrud equation for calculating the mass transfer constants for plant objects with a complex internal structure was shown. Comparison of the particle sizes, the degree of crystallinity, and the calculated mass transfer constant makes it possible to suggest that it is the disordering of pore walls and their subsequent collapse that changes the diffusion mechanism. Schemes of resveratrol fluxes were proposed for extraction from particles of a plant matrix of different sizes; the mass transfer constants were calculated using these data. It was shown that the mass transfer constant has a maximum depending on the disordering of the crystalline structure of plant materials. By disordering the plant matrix, it is possible to increase the flow of matter by seven times. At high crystallinity index, the mass transfer process is impeded by diffusion through the cell wall. Intensive grinding leads to deep disordering of the structure and collapse of pores—the main diffusion channels.