The reaction between W(NMe2)6 and HOCMe2CMe2OH (pinacol, 3 equiv) in ether/hexanes yields the pale yellow compound W(OCMe2CMe2O)3 (1) as pale yellow cubic crystals. Crystal data at -155-degrees-C : a = 16.841(2) angstrom, b = 9.878(1) angstrom, c = 13.373(1) angstrom, beta = 109.60(1)degrees, Z = 4, d(calcd) = 1.69 g cm-3, space group C2/c. The molecule has a crystallographically imposed C2 axis of symmetry but may basically be described as having a distorted octahedral WO6 core, W-O = 1.92(1) angstrom (average). Variable-temperature H-1 NMR data reveal two Me proton signals (+80 to -80-degrees-C) in toluene-d8 and thus indicate that enantiomerization via a trigonal prismatic intermediate is slow on the NMR time scale. The preference for the d0-octahedral WO6 geometry is explained on the basis of oxygen P(pi) to W d(pi) bonding, and these results are compared with those for other d0-ML-6 complexes and d0-M(chelating ligand)3 complexes.