Homoleptic selenolates of V(II) and V(IV) are prepared by selenolysis of the amide ligands in [(Me3Si)(2)N](2)VSeSi-(SiMe3)(3) with 2 equiv of HSeSi(SiMe3)(3). The products were isolated by fractional crystallization from a mixture of hexanes/HMDSO (HMDSO = hexamethyldisiloxane), which first gave a V(II) selenolate of empirical composition V[SeSi(SiMe3)(3)](2)(HMDSO)(1/2), followed by the more soluble monomeric V(IV) species, V[SeSi(SiMe3)(3)](3)"). These compounds are proposed to be the disproportionates of a V(III) precursor (i.e. "V[SeSi(SiMe3)(3)](3)"). Room-temperature EPR spectra of the tetraselenolate exhibited an 8-line pattern typical of V(IV) with g(iso) = 1.92 and A(iso) = 65 G. Addition of 2 equiv of DMPE (DMPE = 1,2-bis(dimethylphosphino)ethane) to the V(II) selenolate afforded trans-(DMPE)(2)V[SeSi(SiMe3)(3)](2) which has been characterized by X-ray crystallography. "VL[SeSi(SiMe3)(3)](3)" can be generated in cold hexanes and trapped with Lewis bases to afford the 4-coordinate adducts V[SeSi(SiMe3)(3)](3)(L) (L = pyridine, 2,6-dimethylphenylisocyanide). For L = pyridine, addition of styrene oxide resulted in a 2-electron oxidation and formation of diamagnetic OV[SeSi(SiMe3)(3)](3). Reaction of (1)/(2) equiv of pyrazine with "V[SeSi(SiMe3)(3)](3)" gave the pyrazine-bridged dimer {V[SeSi(SiMe3)(3)](3)}(2)-(mu-pyrazine) which was also crystallographically characterized.