This article focuses on the Na2O-Ga2O3-TiO2 system, which is barely explored in the study of transparent conductive oxides (TCOs). NaxGa4+xTin−4−xO2n−2 (n = 5, 6, and 7 and x ≈ 0.7–0.8) materials were characterized using neutron powder diffraction and aberration-corrected scanning transmission electron microscopy. Activation energy, as a function of different structures depending on tunnel size, shows a significant improvement in Na+ ion conduction from hexagonal to octagonal tunnels. New insights into the relationship between the crystal structure and the transport properties of TCOs, which are crucial for the design and development of new optoelectronic devices, are provided.