<p>Arylhydrazone ligands Hsal-bzh (<b>I</b>), Hcsal-bzh (<b>II</b>), Hbsal-bzh (<b>III</b>), and Hnsal-bzh (<b>IV</b>) were synthesized using ethyl benzoate, hydrazine hydrate, salicylaldehyde and its 5-substituted –Cl, –Br, and –NO₂ derivative from refluxing methanol. Carefully characterized ligands <b>I-IV</b>, were reacted with appropriate vanadium precursor to isolate the oxidomethxidovanadium(V) complexes [VO(sal-bzh)(CH₃OH)(OCH₃)] (<b>1</b>), [VO(csal-bzh)(CH₃OH)(OCH₃)] (<b>2</b>), [VO(bsal-bzh)(CH₃OH)(OCH₃)] (<b>3</b>) and [VO(nsal-bzh)(CH₃OH)(OCH₃)] (<b>4</b>) as well as dioxidovanadium(V) complexes K[V^VO₂(sal-bzh)] (<b>5</b>), K[V^VO₂(csal-bzh)] (<b>6</b>), K[V^VO₂(bsal-bzh)] (<b>7</b>) and K[V^VO₂(nsal-bzh)] (<b>8</b>). A number of techniques like ⁵¹V NMR, ¹H NMR, ¹³C NMR, single crystal X-ray analysis, HR-MS analysis were performed to confirm the molecular structure of the vanadium(V) complexes in solid state as well as in solution. Dioxidovanadium(V) complexes <b>5–8</b> show good catalytic performance towards the homogeneous epoxidation of a series of olefins with high TOF values. Electron-rich and sterically accessible olefins indene exhibit the highest substrate conversion (94%) with very high TOF values of 3.032 × 10³ h⁻¹, and the least reactivity is observed in electronically poor allylbenzene. Generally, catalysts with the electron-withdrawing group at the 5-position of salicylaldehyde in <b>6–8</b> exhibit marginally better performance than catalysts with unsubstituted salicylaldehyde. During the catalytic reaction, the formation of oxidoperoxymonocarbonatevanadium(V) {[V^VO₂(OCO₃H)(nsal-bzh)] + H} intermediate, which is supposed to be the key component for epoxidation, was identified by ⁵¹V NMR and confirm by HR-MS analysis.</p>