New extractant and an extractant system are attractive for liquid-liquid extraction. To improve the extraction efficiency and selectivity, the binary extractant system consisting of bis-2-ethylhexyl phosphoric acid (D2EHPA) and 2-ethylhexylphosphonic mono-2-ethylhexyl (PC88A) was explored to separate vanadium (V) via synergism from multi-element sulphuric acid leaching solution in this study. The optimal proportion and concentration of extractant was investigated and results demonstrated that the maximum synergistic co-efficient was 1.52 by adjusting the volume ratio to 14:6 (D2EHPA/PC88A) when the extractant concentration was 20% (v/v). Next, the selectivity of the mixture was investigated at different pH values and contact time, which demonstrated better separation of vanadium from primary impurities compared with extraction by D2EHPA or PC88A alone. Furthermore, the Fourier Transform Infrared (FT-IR) spectra were employed to analyse the mechanism of extraction. The results suggested that the cation exchange (P-OH bands) and coordination reaction (P=O bands) contribute to vanadium extraction, and the structure of extracted complex was proposed. The formation of a dimer between D2EHPA and PC88A was demonstrated. Finally, after multi-stage counter-current extraction and stripping, V2O5 product with a high purity of 99.07% was obtained by oxidation, precipitation and calcination. (C) 2017 Published by Elsevier B.V.