We report electron localization of polyoxomolybdates with epsilon-Keggin structure investigated by solid-state Mo-95 NMR and DFT calculation. The polyoxomolybdates studied are the basic epsilon-Keggin crystals of [Me3NH](6)[H2Mo12O28(OH)(12){MoO3}(4)]center dot 2H(2)O (1), the crystals suggested to have a disordered {epsilon-Mo-12} core of [PMo12O36(OH)(4){La(H2O)(2.75)Cl-1.25}(4)]center dot 27H(2)O (2), and the paramagnetic Keggin crystals of [H2Mo12O30(OH)(10){Ni(H2O)(3)}(4)]center dot 14H(2)O (3). The spectra of Mo-95 static NMR of these samples were measured under moderate (9.4 and 11.7 T) and ultrahigh magnetic fields (21.8 T). From spectral simulation and quantum chemical calculation, the NMR parameters of the chemical shift and quadrupole interactions for Mo-95 were estimated. By the analysis based on the result for 1, it was found for 2 that although the {epsilon-Mo-12} core is disordered, the eight d(1) electrons in it are not completely localized on four Mo-Mo bonds. Furthermore, it was shown for 3 that the d(1) electrons are localized to make the Mo-Mo bonds, while the unpaired electrons are also almost localized on the paramagnetic Ni-II ions.