The monooxovanadium(V) complex of composition [VO(OC(6)H(3)(NO(2))(2)-2,4)3] (I) was synthesized by the reaction of VOCl(3) with Me(3)SiOC(6)H(3)(NO(2))(2)-2,4 in toluene and characterised by elemental analyses, molar conductance, and IR, (1)H-and (13)C-NMR, and mass spectral studies. The reactions of (I) with alkali metal 2,4-dinitrophenoxides [MOC(6)H(3)(NO(2))(2)-2,4] (M = Li, Na, K) yield complex salts of composition M[VO(OC(6)H(3)(NO(2))(2)-2,4](4) authenticated by physicochemical and IR spectral studies. Thermal behaviour of complexes was studied by TG and DTA techniques. The molecular modelling calculations of the parent complex and its complex salts were performed to visualise the probable geometry around vanadium metal, which, coupled with spectroscopic evidence, suggests a distorted tetrahedral and a trigonal-bipyramidal geometry for respective complexes.