Germanium was extracted from coal dust by manganese dioxide oxidation-hydrochloric acid distillation, and then germanium dioxide with high purity was obtained via purification process. Meanwhile, gallium in the coal dust dissolved fully into germanium distillation residual liquid. After the filtering process, gallium and residual germanium got into the vinasse. The vinasse acidity was adjusted to 5.6 mol/L to extract gallium by 260# solvent oil solution of tributyl phosphate (TBP). A small amount of germanium in the vinasse was extracted as well, and subsequently went into the organic phase. Then sodium hydroxide solution was taken to conduct re-extraction. Afterwards, its pH was adjusted to 6.5~6.7 and it was heated up to 85~95 oC to hydrolyze gallium and germanium. As a result, hydrogen gallium oxide precipitation and germanium dioxide precipitation were produced. Finally germanium and gallium concentrates were obtained via filtering and drying process. By taking the above procedures, the distillation recovery rate of germanium is as high as 92.37%, and the recovery rate of germanium in the vinasse is 86.18%. Hydrochloric acid leaching rate of gallium is above 81.23% and tributyl phosphate recovery rate and re-extraction rate of gallium is 98.81% and 99.11%, respectively. And the neutralized precipitation straight yield rate is 93.20%. Thus, the hydrochloric acid distillation-tributyl phosphate extraction process is a kind of economic and efficient extraction method, enjoying the qualities of short procedures, easier process control, high recovery rate, less time and less assumption of material.