Synthetic routes to vanadium(V)-phosphinimide derivatives are addressed. Initial synthetic efforts afforded the known compound formulated as VCl2(NPPh3)(3) which was crystallographically determined to be the salt [VCI(NPPh3)(3)]Cl (1). Reactions of the vanadium-imide precursors VCl3(NAr) (Ar = Ph, C6H3-2,6-iPr(2)) with R3PNSiMe3 (R = Ph, iPr, tBu) afforded VCl2(NPh)(NPPh3) (4), VCl2(NPh)(NPiPr(3)) (5), VCl2(NPh)(NPtBu3) (6), VCl2(NC6H3-2,6-iPr(2))(NPPh3) (7), VCl2(NC6H3-2,6-iPr(2))(NPiPr(3)) (8), and VCl2(NC6H3-2,6-iPr(2))(NPtBu3) (9) in yields ranging from 72% to 84%. Subsequent alkylation or arylation reactions resulted in VMe2(NC6H3-2,6-iPr(2))(NPtBu3) (10), Vph(2)(NPh)(NPtBu3) (11), VPh2(NC6H3-2,6-iPr(2))(NPiPr(3)) (12), and VPh2(NC6H3-2,6-iPr(2))(NPtBu3) (13) while substitution reactions with Li[N(SiMe3)(2)] and Li[SBn] gave VCI(N(SiMe3)(2))(NPh)(NPtBu3) (14) and V(SBn)(2)(NC6H3-2,6-iPr(2))(NPtBu3) (15) in yields ranging from 40% to 49% yield. Polarization of the N-P phosphinimide bond and V-N multiple bond character are evidenced by crystallographic data.