Under the optimised experimental conditions of buffer pH 3.4; V(V) was determined quenchofluorimetrically in aqueous medium using a natively fluorescent Bathophenanthroline [ lambda ex(max) = 284.8 nm; lambda em(max) = 446.4 nm ] at room temperature. The fluorescence quenching versus V(V) concentration graph is linear between 2 ng/mL and 0.7 mu g/mL. The quenching action of V(V) upon Bathophenanthroline is rather instantaneous and fluorescence intensity is stable upto 24 h. S.D. and R.S.D. are respectively +/-0.895 ng/mL and 0.894% [11 replicates, 0.1 mu g/mL V(V)]. Large excesses of over 60 cations, anions and some complexing agents were found to have no interference. Only Cu(II), Ni(II) and Co(II) interfere which, however, are easily removed by using a quick ion exchange step. The method has been successfully applied to several synthetic mixtures, Certified Reference Materials (alloys) and environmental water and sewage sludge samples.