Multinuclear (1H, 31P, and 7Li) NMR was applied to understand the ion dynamics in silica-based iongels with a fluorine-free ionic liquid (IL), tetrabutylphosphonium 2-2-(2-methoxyethoxy)ethoxy acetate, [P4,4,4,4][MEEA], doped with 10 and 30 mol % of LiMEEA. The results were compared with bulk [P4,4,4,4][MEEA]/LiMEEA electrolytes and those confined in the “hard” silica matrix of a porous glass. It was found that lithium ion (Li+) local dynamics and Li+ diffusion coefficients are strongly affected by confinements in an iongel and in the porous glass, as was revealed from the analysis of NMR parameters, such as diffusion decays (DDs) in 7Li PFG NMR spectra, broadening of the 7Li NMR resonance lines and variations in the 31P and 7Li chemical shifts. However, NMR diffusometry data does suggest that the studied electrolytes in the iongel confinement yet have properties like bulk electrolytes: (i) high ion diffusivities, (ii) weak alterations of Vogel-Fulcher-Tammann (VFT) parameters for diffusion; and (iii) high transport numbers of ions. The diffusion coefficients of the [MEEA]- anion and the [P4,4,4,4]+ cation are comparable in the bulk, while they are significantly different in the iongels: The specific interactions of the [P4,4,4,4]+ cations with the negatively charged silica matrix slowed down diffusivities of the cations, while almost no effect of the matrix on diffusivities of the [MEEA]- anions was noticed. It was also found that the tortuosity of the iongel channels has a negligible effect on diffusivities of ions. The lithium complexation or/and solvation shells of Li+ ions remained unaffected. Thus, the ionic liquid-based iongel electrolyte acquired the advantages of a semi-solid phase and offered transport properties of a liquid electrolyte.