Microwave-assisted extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometer (MAE—HPLC—ICP—MS) method was developed to determine the contents of arsenic species in rice. Treatments in optimal conditions of 80 ℃, microwave power of 600 W, for 20 min, As(Ⅲ), DMA, MMA, As(Ⅴ) could be completely extracted. Linear correlations of As(Ⅲ), DMA, MMA, As(Ⅴ) were satisfactory. Recoveries was between 86.15%～109.80%. The determination of As(Ⅲ), DMA and As(Ⅴ) by the proposed method in this study was comparable to that by national standard (GB/T 5009.11—2014). MMA determined by this proposed method was higher than that by national standard, indicating a better extraction. Our results showed that different arsenic species could be detected in both raw and cooked rice, and the proportions of As(Ⅲ) and DMA were found declined, but As(Ⅴ) and MMA increased in the latter respectively. The total arsenic content decreased during cooking by 8.77%.