Liquid-liquid extractions of zirconium(IV) from aqueous HCl solutions by mixtures of Aliquat 336 or Alamine 336 and diocytl sulfoxide (DOSO) in the diluent benzene has been found to be always higher than that by any single extractant. While the cationic extractants extract Zr(IV) above 6M HCl, DOSO extracts from 4M onwards. Synergism has been observed in all cases. With any of these extractants extraction becomes almost quantitative at and above 10M HCl, but with mixtures of the cationic and neutral extractants, extraction is quantitative in the range 8–9M HCl. Although the extracted species with DOSO alone seems to be ZrCl4·DOSO, with the mixture of extractants, however, the extracted species appear to be Q2ZrCl6·DOSO where Q is R3+NH (for Alamine 336) and R3+N(CH3) (for Aliquat 336). Studies on separation of95Zr–95Nb pair from aqueous HCl media by Alamine 336 or DOSO and their mixtures in benzene exhibit preferential extraction of95Nb leaving behind95Zr in the aqueous phase, and extractions have been found to depend both upon the extractant and HCl concentrations.