Metal catalyzed reactions are a powerful tool to design new chemical synthetic processes according to Green Chemistry principles, such as pollution prevention, atom economy, catalysis and the use of safer solvents and chemicals. The selection of the metal is particularly important to plan relevant and applicable processes: in particular, Vanadium is a good choice because it is cheap, naturally abundant and relatively non-toxic. Moreover, its rich redox chemistry makes it a suitable catalyst for a number of different reactions. A survey of catalytic vanadium-catalyzed oxidations investigated by our group in the last ten years is presented. Changing the ligand and the reaction conditions, the selective oxidation of model alkenes and sulfides and the oxidative bromination of alkenes, alkynes and toluene were successfully obtained. The introduction of substituent groups on the ligand scaffold allowed to investigate the ligand effect on the metal core by various techniques. These vanadium based catalytic systems found applications in the desulfurization of model fuel, the design of screen-printed electrodes for monitoring the hydrogen peroxide consumption and in sustainable synthesis. (C) 2016 Elsevier B.V. All rights reserved.