Numerous studies have studied the health risk assessment of human exposure to As or bioaccessible As via rice intake; however, the bioaccessibility of different As species in rice is seldom reported. In the present study, 31 rice samples were collected from markets or individual growers to investigate the speciation and bioaccessibility of As. Five different species (As, As, DMA, MMA, and AsB) were detected in rice samples from different regions, among which As accounted for the largest proportion (62.95% in average), followed by DMA and As. In addition, the cooking method could facilitate the release of As from rice into gastric and intestinal juice, and subsequently increase the bioaccessibility of As. The bioaccessibility of inorganic As in cooked rice ranged from 71.83 to 100%, and that of organic As ranged from 31.69 to 61.04%. Non-carcinogenic and carcinogenic risk assessment of children and adults exposure to As via rice intake considering the bioaccessibility of cooked rice was carried out. The target hazard quotient (THQ) of iAs and total As for children ranged from 0.21 to 1.61 and 0.48 to 2.26, respectively, while those for adults ranged from 0.12 to 0.88 and 0.26 to 1.23, respectively. Incremental lifetime cancer risk (ILCR) for children and adults ranged from 9.57 × 10 to 7.25 × 10 and 5.21 × 10 to 3.95 × 10, respectively. The results of risk assessment indicated that children would face a higher health risk than adults when they took the same type of rice as their staple food.