A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, was interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W-0(PMe3)(6)], [(WCl2)-Cl-II(PMePh2)(4)], [(WCl2)-Cl-III(dppe)(2)][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane), [(WCl4)-Cl-IV(PMePh2)(2)] [W-V(NPh)Cl-3(PMe3)(2)], and [(WCl6)-Cl-VI], correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redoxactive ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio of the L-3,L-2-edges and the L-1 rising-edge energy with metal Z(eff), thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W-IV(mdt)(2)(CO)(2)] and [W-IV(mdt)(2)(CN)(2)](2-) (mdt(2-) = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W1v species even though the mdt ligands exist at different redox levels in the two compounds. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: (1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Zeff in the species of interest. (2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS. (3) Increased care in interpretation if strong pi-acceptor ligands, particularly CO, or pi-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal ligand distances, exaggerate the difference between formal oxidation state and metal Z(eff) or, as in the case of [W-IV(mdt)(2)(CO)(2)], exert the subtle effect of modulating the redox level of other ligands in the coordination sphere.