Li diffusion parameters of a structurally disordered Li-Al-Si-oxide prepared by gas-phase synthesis were complementarily investigated by both time-domain NMR techniques and impedance spectroscopy. The first include 7Li NMR spin-lattice relaxation (SLR) measurements in the laboratory as well as in the rotating frame of reference. An analysis of variable-temperature NMR line widths point to an activation energy E a of approximately 0.6 eV. The value is confirmed by rotating-frame SLR NMR data recorded at approximately 11 kHz. Above room temperature the low-temperature flank of a diffusion-induced rate peak shows up which can be approximated by an Arrhenius law yielding E a = 0.56(1) eV. This is in very good agreement with the result obtained from 7Li spin-alignment echo (SAE) NMR being sensitive to even slower Li dynamics. For comparison, dc-conductivity measurements, probing long-range motions, yield E a = 0.8 eV. Interestingly, lowtemperature SAE NMR decay rates point to localized Li motions being characterized with a very small activation energy of only 0.09 eV. © by Oldenbourg Wissenschaftsverlag, München.