Efficient extraction and stripping for recovering [GRAPHICS] vanadium(V) from the leaching/aqueous solution of chromium bearing vanadium slag (V-Cr slag) are essential to the reuse of heavy metals. The performance characteristics of a new reagent, primary amine N1519, were first reported for extracting vanadium. With a phase ratio of organic to aqueous up to 1:1, 99.7% of vanadium(V) can be effectively extracted from the leaching/aqueous solution, and powder of NH4VO3 was obtained through the stripping with ammonia. The new reagent can be recyclable in use for sustainable reuse after stripping. Different extraction conditions, e.g., the initial pH of the leaching/aqueous solution and the molar quantity of N1519 were investigated. The powder of vanadium-organic compounds (VOC) with N1519 formed in the process of extraction was obtained and purified through three steps of solvent-out crystallizations. The hydrogen bond association mechanism of extraction was illustrated with the structure of VOC and the enthalpy change in extraction process. The fast extraction process and slow stripping procedure for recovering vanadium(V) are suitable for use in annular centrifugal contactors with very short contact/resident times and mixed-settler extractors with very good mass transfer, respectively. The results offer significant advantages over conventional processes.