The effective V(V) and Cr(VI) separation is very difficult due to their similarity in physiochemical properties. In this research, almost completely separation of V(V) and Cr(VI) with primary amine N1923 was firstly demonstrated by employing multistage countercurrent extraction (MCE) with annular centrifugal contactors (ACCs). The optimum operation conditions of single-stage extraction with ACC were determined by systematic experiments, and best conditions of the rotor speed, the flow rate and the flow ratio of organic phase to aqueous phase were obtained. The loaded-organic phase can be reused for extraction process after stripping with ammonia/sodium hydroxide. Vanadium, in the leaching/aqueous solution with the initial pH of 6.1, was reached to extraction equilibrium by three-stage countercurrent extraction with ACCs. V(V) and Cr(VI) were separated through 21 stages of countercurrent extraction with ACCs. 95.1% of vanadium and almost none of chromium were extracted, with the separation factor approaching infinity. Through the mechanism of hydrogen bond association and different species of two metals in the leaching/aqueous solution, an in-depth analysis to correlate the results obtained and the chemical reactions with ACCs has been made in order to establish a firm conclusion with aim of the guidance in industrial application.(C) 2017 Elsevier B.V. All rights reserved.