Fly ash as industrial waste can be divided into coal fly ash and heavy oil fly ash. Since the fly ash contains lost of metallic oxides, it can be treated as a second resource from which various valuable metals may be separated, recovered and refined. The leachants of fly ash are hydrochloric acid, sulfuric acid and water. The heavy oil fly ash contains a high concentration of Ni, V, Ga and so on, while the leaching solution from coal fly ash has poorer contents of soluble metal ions than the heavy oil fly ash. Before the recovery, the adsorption or ion exchange method was used as pre-treatment. For an efficient leaching, two steps were taken to prevent any disturbance from other metal ions. Such extractants as LIX51, TBP(100%), TOPO, TOMAC and D2EHPA were used in order to separate, recover and refine Ga and V from the leaching solution. Gallium was extracted as much as nearly 100% at the concentration of 2M-HCl when used to the concentration of 0.1M TOMAC as extractant, and the extraction of Fe(III) showed a similar tendency. The selective extraction of Ga could be proceeded after Na₂S two times as much as Fe equivalent was added to aqueous solution. The refinement by way of vanadium extraction appeared in the order of TOMA>DP-8R >LIX51 at the range of pH 0-3. The precipitation of co-existent iron ions from raffinate could be removed by controlling pH at 3 or higher.