A process consisting of ball milling followed by NaOH leaching was developed to selectively dissolve alumina from black dross. From the ball milling treatment, it was found that milling speed greatly affected the leaching behavior of silica and the oxides of Ca, Fe, Mg, and Ti present in dross. The leaching behavior of the mechanically activated dross was investigated by varying NaOH concentration, leaching temperature and time, and pulp density. In most of the leaching conditions, only alumina and silica were dissolved, while the leaching percentage of other oxides was negligible. The leaching percentage of silica decreased rapidly to nearly zero as pulp density increased to 100 g/L. At the optimum leaching conditions (5 M NaOH, 50 °C, 2 h, pulp density of 100 g/L), the purity of Al in the leaching solution was higher than 98%, but the leaching percentage of alumina was only 35%.