Pea starch (PS) was subjected to microwave treatment at 280 W for 30, 60, 90, and 120 s to investigate the effects of microwave treatment on its structure, physicochemical properties, and digestibility. Subsequently, particle size, microstructure, crystal structure, ordered structure, thermodynamic properties, rheological properties, and digestion characteristics were analyzed. The results showed that because of water absorption, PS particles expanded as microwave treatment duration increased, leading to increased particle size. The Raman spectrum half-width at 480 cm-1 increased from 16.20 to 20.59, whereas the infrared absorption peak ratio R1047/1022 decreased from 0.58 to 0.36. Crystallinity decreased from 23.74% to 8.46%, indicating a reduction in long-range order. Hydration properties were significantly improved, with water absorption index, swelling degree, and cold-water solubility increasing from 1.94 g•g-1, 1.91%, and 2.04% to 5.34 g•g-1, 12.34%, and 7.81%, respectively. Gelatinization parameters were markedly reduced, with gelatinization enthalpy decreasing from 6.02 J•g-1 to zero. After microwave treatment, PS birefringence was gradually lost; modulus and loss moduli decreased. Digestibility analysis revealed a reduction in resistant starch content from 30.89% to 10.09%. These findings suggest that microwave treatment modifies PS molecular structure, thereby enhancing its solubility and swelling power, reducing gelatinization temperature, increasing thermal stability, and improving its viscoelasticity. Therefore, microwave-treated PS may serve as a potential thickener, stabilizer, and nutrient supplement in green foods. In the green materials sector, PS can be utilized in bioplastics and packaging materials to enhance biodegradability and mechanical properties.