In the present work, a novel, simple, and sensitive method for the direct determination of trace Sb in water samples was developed based on hydrogen-doped solution anode glow discharge-optical emission spectrometry (SAGD-OES). It was found that the vapor generation and excitation of Sb occurred simultaneously in the SAGD, contributing to the significant improvement in the sensitivity of Sb as compared with normal pure He-operated SAGD or solution cathode glow discharge. Besides, the proposed hydrogen-doped SAGD-OES could be operated even at pH = 14, which could reduce the interference of coexisting ions as many metal ions could be precipitated and removed. Our results demonstrated that the proposed method offered good tolerance to the interferences of Li, Na, Ca, Mg, Fe, Ni, Mn, and Zn ions even at a concentration of 50 mg L −1 . Under optimized conditions, the limit of detection of Sb was 0.85 μg L −1 , which was comparable to that of microplasma sources coupled with conventional hydride generation. The linearity of the Sb calibration curve reached R 2 > 0.999 in the 5−5000 μg L −1 range. Finally, the accuracy of the proposed method was validated by the determination of certified reference materials [GSB 07-1376[GSB 07- -2001 (1) and ( 2))] and real water samples. The proposed low-power (6 W), green, sensitive, rapid, and robust method provides a promising approach for on-site trace Sb analysis and may also be extended to other elements.