SummaryThis work established an oxidised porous starch carrier system for the administration of caffeine by selectively oxidising the main hydroxyl groups at the C6 positions of porous starch to carboxyl groups using 2,2,6,6‐tetramethylpiperidoxyl (TEMPO) oxidation. The loading capacity and encapsulation efficiency of oxidised porous starch on caffeine rose as the oxidation degree (0%–90%) increased, increasing by 4.66 and 4.95 times, respectively, at 90% oxidation. The crystallinity of porous starch diminished after TEMPO oxidation, while the crystalline caffeine transferred into an amorphous state when loaded onto oxidised porous starch. Following oxidation, the absolute value of porous starch surface potential rose, enabling the granules avoided aggregation. Caffeine formed tighter bonds with oxidised porous starch in acidic conditions due to the dissociation of carboxyl groups, which lead to a peak loading capacity (8.02%) of oxidised porous starch with 90% oxidation at pH 4. Electrostatic interactions and hydrogen bonds were the driving forces. Long‐term gastrointestinal release of caffeine was achieved utilising oxidised porous starch as carriers.