The fact that vanadium complexes can show catalytic activity in the selective oxidation of cyclohexane, under mild conditions, have led to an increasing interest in its coordination chemistry. Design and synthesis of suitable multidentate ligands could significantly contribute to the understanding and further development of new efficient and selective catalytic V-based systems. Carbohydrazone ligands containing diazine fragment (C=N–N=C) are particularly promising due to the presence of several coordination sites and ability to form stable oxidovanadium complexes of different metal oxidation states. Herein, we describe dinuclear vanadium(V) complexes, namely, NH4[(VO2)2(HL)] (1) and [(VO2)(VO)(HL)(CH3O)] (2), where H4L = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone [1]. The VO2+ entity accommodated in the NNO binding site of the dinucleating ligand provides an axial position for the vanadium (V) atom in the ONO binding pocket of the ligand in the second neighboring complex 1. A similar distribution of roles (functions) is observed in 2, although different entities (VO2+ and VO3+) are found in the ONN and ONO binding sites, respectively. The compounds characterized by single-crystal X-ray crystallography form dimeric associates (dimers of dimers) via two or one V−μ-O−V linkages in the crystal. Compounds 1 and 2 act as homogeneous catalysts for the MW-assisted and solvent-free peroxidative oxidation of cyclohexane, via a radical mechanism, affording cyclohexanol and cyclohexanone in high selectivity and in a yield that is ca. 4 times higher than that of the industrial process. The mild and environmental benign conditions, such as solvent and additive-free protocol, use of environmentally acceptable aqueous oxidant and energy source (MW irradiation), short reaction time are significant features toward the development of a sustainable chemical process for the cyclohexane oxidation.