The synthesis, X-ray crystal structure, spectroscopic, and electrochemical properties of a new tetranuclear vanadium(IV,V,IV,V) complex [(VO) 4 (btppnol) 2 (μ-O) 2 ](ClO 4 ) 2 .2DMF.2H 2 O(1) utilizing the previously described unsymmetrical dinucleating ligand N-(2-hydroxybenzyl)-N,N ' ,N ' -tris(2-pyridylmethyl)-1,3-diaminopropan-2-ol (H 2 btppnol) are reported. The complex comprises two different [V 2 O 3 ] 3 + core structures: one [V 2 O 3 ] 3 + core in a syn-dioxo-μ-O(alkoxo) configurarion and another [V 2 O 3 ] 3 + core in an anti-dioxo-μ-oxo configuration, as well as being composed of non-equivalent vanadium centers as a consequence of the use of an unsymmetrical ligand. This complex represents the first example in the literature of a vanadium complex with this particular structure and its interesting electrochemical and spectroscopic properties were investigated.