We report solid-state Mo-95 NMR of Mo-V, Mo-V,Mo-VI and Mo-VI species in mixed-valence polyoxomolybdates (V, VI) with localized or delocalized d(1) electrons. Parameters about chemical shift and quadrupole interactions of Mo-95 in diamagnetic crystals of [Me3NH](6)[(H2Mo12O28)-O-V(OH)(12)((MoO3)-O-VI)(4)] center dot 2H(2)O(1) with localized electrons and [NMe4](2)[NH4](8)[((Mo6MoO23)-Mo-VI-O-V)(2)] center dot 8H(2)O(2) with delocalized ones were obtained by simulation of magic-angle-spinning (MAS) Mo-95 NMR spectra. The isotropic and anisotropic chemical shifts of sites of Mo-V in 1 and Mo-V,Mo- (VI) in 2, respectively, exhibited absolute values quite larger than those of other Mo-VI sites, which is examined by quantum chemical calculations. (C) 2010 Elsevier B.V. All rights reserved.