This work presented data using always real solutions yielded from the treatment of Spanish raw material, in detail, from a slag obtained in a pyrometallurgy process of tin production from mining tailings containing mainly cassiterite and columbo tantalite. In this investigation the raw material was treated by acid leaching, using HF/H2SO4 as a leaching agent. Then, liquid-liquid extraction of Nb and Ta have performed with Cyanex®923 extractant, further, both metals were separately stripped. Once metals were separated into two aqueous solutions, they were precipitated and calcined to yield the corresponding compounds (Nb2O5 of 98.5% purity and Ta2O5 of 97.3% purity).