The autohydrolysis of Lentinus edodes was proposed for the extraction of components with antioxidant properties. Operation under non-isothermal conditions was evaluated and compared with isothermal heating. The influence of process severity was assessed in the range of 0.18 to 4.89 (temperature between 50 and 250 °C), up to 80% (d.b.) The influence of process severity during the autohydrolysis of Lentinus edodes was assessed in the range −0.3 to 4.89 (temperature between 50 and 250 °C). Up to 80% (d.b.) of the initial raw material could be solubilized at 210 °C. The different behavior of the saccharide and phenolic fractions was observed with the treatment temperature. Whereas the highest concentration of the saccharide components (mainly glucooligosaccharides) was found at 210 °C, the maximum phenolic yield was identified at 250 °C. The phenolic content and the antiradical properties of the extract showed a continuous increase with the temperature range studied, and at 250 °C, showed antiradical properties comparable to synthetic antioxidants. Autohydrolysis liquid fractions were used as solvents in the formulation of bioactive starch-based hydrogels, identifying a positive correlation between the gel softening and the extracts’ bioactivity features.