As a physical method for starch modification, dry heating treatment (DHT) at high temperatures (150 and 180°C, respectively) was applied to blue highland barley (BH) starch with different durations (2 and 4 h). The effects on its multi-structures, physicochemical properties, and in vitro digestibility were investigated. The results showed that DHT had changed the morphology of BH starch, and the diffraction pattern remained an “A”-type crystalline structure. However, with an extension of DHT temperature and time, the amylose content, gelatinization temperature, enthalpy value, swelling power, and pasting viscosity of modified starches decreased, while the light transmittance, solubility, and water and oil absorption capacities increased. Additionally, compared with native starch, the content of rapidly digestible starch in modified samples increased after DHT, whereas those of slowly digestible starch and RS decreased. Based on these results, the conclusion could be drawn that DHT is an effective and green way to transform multi-structures, physicochemical properties, and in vitro digestibility of BH starch. This fundamental information might be meaningful to enrich the theoretical basis of physical modification on BH starch and extend the applications of BH in the food industry.