There has been an increasing demand for scandium (Sc). However the supply is insufficient because the separation and recovery of Sc as a byproduct from ores is difficult. In this study, extraction and separation of Sc<sup>3+</sup> from a sulfuric acid solution containing transition metals such as Al<sup>3+</sup>, Fe<sup>3+</sup>, Mn<sup>2+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup> and Zn<sup>2+</sup> was investigated using a β-diketone, HTTA and a neutral extractant, TOPO. Due to the synergistic effect with the two extractants, Sc<sup>3+</sup> was effectively and selectively separated even from Fe<sup>3+</sup>, the separation of which is difficult with HTTA alone. The extraction mechanism was examined and it was revealed that Sc<sup>3+</sup> is extracted with three HTTA and one TOPO molecules. Scandium was readily stripped from the extracting phase by 1 M sulfuric acid. The potential use of the combination of the β-diketone with TOPO for the recovery of Sc<sup>3+</sup> in a refining process was demonstrated.