Summaryβ-glucan is the major component of the extracellular matrix (ECM) of many fungi, including wood degrading fungi. Many of these species also secrete oxalate into the ECM. Our research demonstrates that β-glucan forms a novel, previously unreported, hydrogel at room temperature with oxalate. Oxalate was found to alter the rheometric properties of the β-glucan hydrogels, and modeling showed that β-glucan hydrogen bonds with oxalate in a non-covalent matrix. Change of oxalate concentration also impacted the diffusion of a high-molecular-weight protein through the gels. This finding has relevance to the diffusion of extracellular enzymes into substrates and helps to explain why some types of wood-decay fungi rely on non-enzymatic degradation schemes for carbon cycling. Further, this research has potential impact on the diffusion of metabolites in association with pathogenic/biomedical fungi.