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Β-glucan is a strongly hydrophilic non-starchy polysaccharide, which, when incorporated in food, is renowned for its ability to alter functional characteristics such as viscosity, rheology, texture, and sensory properties of the food product. The functional properties of β-glucans are directly linked to their origin/source, molecular weight, and structural features. The molecular weight and structural/conformational features are in turn influenced by method of extraction and modification of the β-glucan. For example, whereas physical modification techniques influence only the spatial structures, modification by chemical agents, enzyme hydrolysis, mechanical treatment, and irradiation affect both spatial conformation and primary structures of β-glucan. Consequently, β-glucan can be modified (via one or more of the aforementioned techniques) into forms that have desired morphological, rheological, and (bio)functional properties. This review describes how various modification techniques affect the structure, properties, and applications of β-glucans in the food industry.