Abstract Oats do not contain gluten protein, and oat dough structure is formed mainly through the hydrogen bonding of starch and β‐glucan. As a non‐thermal processing technology, high hydrostatic pressure (HHP) is mainly used to modify starch and protein in food processing. This study investigated the effects of HHP treatment on the morphological, structural, thermal, pasting and in vitro digestion properties of oat starch/β‐glucan mixtures. Results showed that β‐glucan interconnects with amylose through hydrogen bonding and has a protective effect on the crystalline region of oat starch. Effect of HHP treatment on the crystal structure of mixture system goes through crystal structure perfection stage, crystallisation disintegration and gelatinisation stage. After 300–400 MPa treatment, the changes in particle surface were not obvious, the phase transition temperature, the ΔH gel and the PT of mixtures increased, while the particle size, viscosity and BD values decreased. After 500–600 MPa treatment, mixtures were completely gelatinised, most of the particles swelled and deformed, the particle size increased significantly. The principal component analysis results show that the complexes were distributed in the same region with similar properties after the 300–400 MPa and 500–600 MPa treatments, respectively.