The liquid–liquid extraction of V(V) from a nitrate medium by tri-n-Octylamine [(n–C₈H₁₇)₃N; abbreviated as TOA] dissolved in distilled colorless kerosene has been investigated as a function of various experimental parameters. The equilibration time is less than 10 min. It is observed that the extraction ratio increases with increasing [V(V)] in the aqueous phase, which is possibly a result of the formation of V₁₀O₂₆(OH) ₂ ⁴⁻ (via reaction: 10 VO₂ ⁺ + 8 H₂O → V₁₀O₂₆(OH) ₂ ⁴⁻  + 14 H⁺) with increasing concentration in the aqueous phase. The nature of the species extracted into the organic phase depends on the existing aqueous species prevailing at a certain pH. At lower pH values, the extraction of VO₂ ⁺ occurs via cation (H⁺) exchange of (C₈H₁₇)₃NHNO₃. On the other hand, at higher pH values, anionic V(V) species such as V₁₀O₂₆(OH) ₂ ⁴⁻ , V₁₀O₂₇(OH)⁵⁻, V₁₀O₂₈ ⁶⁻ etc. are extracted by solvated ion-pair formation mechanism. The TOA concentration dependence varies from 2 at a lower pH region (~2.3) to 1 at a higher pH region (~5.7). The extraction is also found to be favored by a rise of nitrate concentration in the aqueous phase. Temperature has a pronounced effect with ΔH < −58 kJ/mol. Kerosene is demonstrated as the best diluent for this system. Increased organic to aqueous phase volume ratio (O/A) enhances extraction ratio. The extracted species can be stripped by 0.75 mol/L NH₄OH solution to the extent of 72% in a single stage. But stage-wise stripping is not so effective. It is observed a very high loading, of the order of ~2.3 mol V(V) per mol TOA.