Lithium-oxygen batteries have gained prominence in recent years due to their potential advantages over conventional lithium-ion batteries, including higher energy density, cost-effectiveness and environmental sustainability. To fully exploit these advantages, it is essential to understand the interplay between porous carbon electrode materials and electrolytes in these devices. This study presents a nuclear magnetic resonance investigation of the confined LiTFSI (lithium bis(trifluoromethanesulfonyl)imide) - TEGDME (tetraethylene glycol dimethyl ether) electrolyte within carbonaceous materials with different pore sizes. Three carbon materials (microporous, mesoporous, and hierarchical) were synthesized from the same precursor to ensure equivalent surface chemistry, which was verified by X-ray photoelectron spectroscopy. The dynamics and distribution of solvent and Li ions in the different pores were studied by