The thermal denaturation of rice structure and its starch crystalline/amorphous structure was studied by mid-infrared (MIR) spectroscopy and two-dimensional mid-infrared (2D-MIR) spectroscopy. The results indicated that the infrared absorption modes of rice starch included νOH-rice, νasCH2-rice, νsCH2-rice, νamide-Ⅰ-rice, νamide-Ⅱ-rice and νC-O-rice. As the measurement temperature increased (303-393 K), the sensitivity of rice starch crystals/amorphous structures to heat and the order of change were different from those in different origins. Further research on the relevant mechanism shows that there are some differences in heat resistance of different rice starch crystal/amorphous structure, which further affects its taste. The study expanded the scope of research on the thermal denaturation of rice structure and its starch crystals/amorphous structures using MIR spectroscopy and 2D-MIR spectroscopy.