The feasibility of selective recovery of titanium and scandium from a high acidic content lixivium by solvent extraction was verified in this study. Amongst the extractants, which were investigated for the selective extraction of scandium and titanium from the acidic lixivium in this study, D2EHPA and primary amine N1923 performed best. 2-Octanol and sulfonated kerosene were used as modifier and diluents, respectively, scandium and titanium were stepwise extracted by D2EHPA and primary amine N1923. More than 98% of scandium was extracted selectively by using 10% (v/v) D2EHPA, 5% (v/v) 2-octanol, and 85% (v/v) sulfonated kerosene under the O/A ratio of 1 :6 for 5 min. After the purification processes, the Sc2O3 with a purity of 99.9% was obtained. More than 96% of titanium was extracted selectively by using 10% (v/v) N1923, 5% (v/v) 2-octanol, and 85% (v/v) sulfonated kerosene under the O/A ratio of 2:1 for 5 min. After the process of scrubbing and stripping, a concentration of titanium solution of 64.1 g/L was obtained. Finally, a solvent extraction flowsheet was established.