Precious metals are currently associated with selenium (naumannite, Ag2Se) and tellurium (calaverite, AuTe2; sylvanite, (Au,Ag)2Te4) to form species refractory to cyanidation. The aim of this preliminary work was to study the use of the solvent extraction technique to recover tellurium and selenium ions from a synthetic solution similar to the cyanidation effluents to recycle the free cyanide back to the process. For the extraction of the Se and Te anions, the use of quaternary amines as extractants was evaluated (tallow trimethyl ammonium chloride, Quartamin TPR; hexadecyl trimethyl ammonium chloride, Amine F; and trioctyl methyl ammonium chloride, Aliquat 336) employing nonylphenol as a modifier in the organic phase (iso-octane). The results obtained showed that the extraction was strongly affected by the pH and that it was possible to recover up to 83% of Se and 10% of Te with Quartamin TPR from two synthetic solutions containing 23 mg/L of Te and 20 mg/L of Se with a molar cyanide:metal ratio of 1:4 at pH 11, a ratio of aqueous/organic (A/O) = 1 (V/V) and an extractant concentration of 0.022 mol/L. A maximum distribution coefficient (D) of 4.97 was obtained at pH 11. The McCabe-Thiele diagram indicates that two theoretical extraction stages are necessary to obtain a good extraction of Se complexes using Quartamin TPR.