The pyrolysis characteristics of cadmium (Cd)-impregnated cellulose, hemicellulose, and lignin were studied to elucidate the pyrolysis velocity and deoxygenation characteristics of Cd-contaminated rice straw. The results show that Cd significantly affects the pyrolysis characteristics of a single biomass component. With a heating rate of 5 °C·min−1 and a Cd loading of 5%, the initial pyrolysis temperature of cellulose and hemicellulose decreases while that of lignin increases. The maximum pyrolysis velocity of cellulose, hemicellulose, and lignin is decreased by 36.6%, 12.4%, and 15.2%, respectively. Cd increases the pyrolysis activation energy of the three components and inhibits their deoxygenation. For the pyrolysis of Cd-contaminated rice straw, both the initial depolymerization temperature and the pyrolysis velocity of hemicellulose is reduced, while the pyrolysis velocity of cellulose is accordingly increased. When Cd loading amplifies to 0.1%, 1%, and 5%, the maximum pyrolysis velocity of hemicellulose is decreased by 7.2%, 10.5%, and 21.3%, while that of cellulose is increased by 8.4%, 62.1%, and 97.3%, respectively. Cd reduces the release of volatiles and gas from rice straw, such as CO2, CO, and oxygen-containing organics, which retains more oxygen and components in the solid fraction. This research suggested that Cd retards the pyrolysis velocity and deoxygenation of rice straw, being therefore beneficial to obtaining more biochar.