The electron transfer series of complexes [V((t)bpy)(3)](z) (z = 3+, 2+, 0, 1-) has been synthesized and spectroscopically characterized with the exception of the monocationic species. Magnetic susceptibility measurements (4290 K) establish an S = 1 ground state for [V((t)bpy)(3)](3+), S = 3/2 for [V((t)bpy)(3)](2+), S = 1/2 for [V((t)bpy)(3)], and an S = 0 ground state for [V((t)bpy)(3)](1-). The electrochemistry of this series recorded in tetrahydrofuran solution exhibits four reversible one-electron transfer steps. Electronic absorption, X-band electron paramagnetic resonance (EPR), and V K-edge X-ray absorption (XAS) spectra were recorded. All complexes have been studied computationally with density functional theory (DFT) using the B3LYP functional. It is unequivocally shown that the electronic structure of complexes is best described as [V-III(tbpy(0))(3)](3+), [V-II((t)bpy(0))(3)](2+), [V-II((t)bpy(center dot))(2)((t)bpy(0))](0), and [V-II((t)bpy(center dot))(3)](1-), where ((t)bpy(0)) represents the neutral form of the ligand and ((t)bpy(center dot))(1-) is the one-electron reduced mononanionic radical form. In the neutral and monoanionic members, containing two and three ((t)bpy(center dot))(1-) ligands, respectively, the ligand spins are strongly antiferromagnetically coupled to the spins of the central V(II) ion (d(3); S = 3/2) affording the observed ground states given above.