Objective: Establishing an analysis method for the detection of six arsenic compounds trivalent arsenic, pentavalent arsenic, methyl arsenic, dimethyl arsenic, arsenical choline and arsenical betaine in urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and providing a theoretical basis for health assessment of arsenic poisoning patients. Methods: HPLC-ICP-MS was used to detect six arsenic compounds with the hamilton PRP-X100 column and aqueous ammonium phosphate in a gradient elution as mobile phase. Results: There was a good linear relationship in the selected range of six arsenic compounds evidenced by a linear correlation coefficient greater than 0.999. The detection limit of 6 arsenic compounds was 0.46~0.57 μg/L, and the minimum quantitative concentration were 1.52~1.91 μg/L. The recovery rates of six arsenic compounds were 96.5%~106.4%, The within-run and between-run relative standard deviation was 2.9%~6.2% and 3.8%~8.7%. Conclusion: The established method with high accuracy and precision is suitable for detecting arsenic levels in urine of occupational arsenic exposure population.