This study investigated the physicochemical modifications of cooked rice caused by adding various supplements (rapeseed oil, dried wasabi powder, and dried chili pepper powder). The physicochemical and digestive properties of treated cooked rice were analyzed using multiple techniques to determine the impact of supplements on the rice quality, including its starch digestibility. All samples with added supplements showed an increase in surface firmness (0.77–0.95 kg·m/s2 (N)) and a decrease in thickness (2.23–2.35 mm) and surface adhesiveness (1.43–7.22 J/m3). Compared to the control group, two absorption peaks at 2856 and 1748 cm−1 and new signals at 1683 and 1435 cm−1 appeared in the Fourier transform infrared (FTIR) spectroscopy. Analysis of FTIR results revealed that the interaction force was mainly through noncovalent interactions. Moreover, adding supplements increased the resistant starch (RS) levels in all samples. Scanning electron microscopy (SEM) suggested that oil-enriched phases, proteins, and polyphenols could cause large agglomeration and loose gel structure. These results suggested the formation of amylose-guest molecule complexes, which may influence starch functionality. Our work could provide insight into the starch–supplement interactions and the key factors affecting starch digestibility.