In this paper, the influence of ball-milling on the structure and hydrogen absorption-desorption behavior of Zr50.7Cu28Al12.3Ni9 metallic glass powders produced by gas atomization were studied. The as-atomized metallic glass powders were ball-milled for 80 h. It is found that the powders remain amorphous state after the ball-milling process. The effects of ball-milling on the hydrogen absorption-desorption behavior of the metallic glass powders were measured with an automatic Sieverts apparatus. After the ball-milling, the hydrogen absorption behavior of the metallic glass powders is improved. In addition, the hydrogen absorption capacity of the ball-milled metallic glass powders increases to 2.66 wt.% (H/M≈1.9) from 0.96 wt.% (H/M≈0.7) of the as-atomized metallic glass powders. However, the hydrogen desorption behavior of the ball-milled metallic glass powders is still poor due to the formation of very stable hydride.