Abstract Recovery of vanadium from a spent catlaysts leaching process has been studied using primary amine PRIMENE 81R, resulting in an industrial multistage process for the treatment of these effluents. An extraction mechanism for V(V) is proposed for this amine in acidic media, verifying the influence of pH on the process. Adequate ranges for the variables: O/A ratio, organic phase composition, pH, stirring speed and phase separation speed were fixed and simulated in industrial conditions. Vanadium is finally recovered by means of precipitation as ammonium metavanadate and later calcination to obtain vanadium pentoxide of commercial grade. ACKNOWLEDGMENTS The authors wish to thank to ROHM & HAAS for the free samples of PRIMENE 81R amine.