This study investigates the effect of Na content on the structural, optical, and electrical properties of sol-gel Na-doped ZnO films using x-ray diffraction, photoluminescence, and conductivity measurements. It is shown that a p-type conversion of the Na-doped ZnO film might be due to a combined effect of the increased substitutional-Na density and the decreased oxygen-vacancy (VO) density. However, excess Na incorporation into ZnO shows an ambiguous carrier type due to the increase in the donorlike VO density. These results indicate that compensation effects limit the hole concentration in the Na-doped ZnO films. In addition, when more Na is substituted into the ZnO system, the difference in the ionic radii of Zn2+ and Na+ starts playing an increasingly important role, causing the presence of tensile stress in the Na-doped ZnO film.