Reactions of VCl₄ with one mol equiv. of L–L (L–L = MeSe(CH₂)₂SeMe, MeSe(CH₂)₃SeMe, ⁿBuSe(CH₂)₂SeⁿBu) in anhydrous CH₂Cl₂ solution at room temperature give [VCl₄(L–L)] as very moisture-sensitive dark purple solids. Using VCl₄ and excess selenoether in gently refluxing CH₂Cl₂ leads to reduction to [VCl₃(L–L)] (L–L as above and o-C₆H₄(CH₂SeMe)₂), while VCl₄ reacts with excess SeMe₂ at room temperature to give [VCl₃(SeMe₂)₂]. All new complexes were characterised by microanalysis, IR and UV/visible spectroscopy and magnetic measurements. Reaction of [(Cp)₂VCl₂] with two mol equiv. of LiSe^tBu in anhydrous thf gives the V^IV selenolate complex [(Cp)₂V(Se^tBu)₂] as a very moisture-sensitive brown solid. The new complexes have been investigated as possible reagents for deposition of vanadium selenide. While low pressure chemical vapour deposition (LPCVD) experiments showed that the diselenoether complexes were not sufficiently volatile for VSe₂ deposition, [VCl₃(SeMe₂)₂] gives very thin deposits of VSe₂. LPCVD studies on [(Cp)₂V(Se^tBu)₂] at 600 °C produce thicker black films of VSe₂. In all cases EDX measurements show that the films are Se deficient.