Spectroscopic ellipsometry (SE) has been applied to study the effects of grain boundary, humidity, and surface texture on the carrier transport properties of Al-doped ZnO layers fabricated by dc and rf magnetron sputtering. In the SE analysis, the variation in the free carrier absorption toward the growth direction, induced by the ZnO grain growth on foreign substrates, has been modeled explicitly by adopting a multilayer model in which the optical carrier concentration (Nopt) varies continuously with a constant optical mobility (μopt). The effect of the grain boundary has been studied by comparing μopt with Hall mobility (μHall). The change in μHall/μopt indicates a sharp structural transition of the ZnO polycrystalline layer at a thickness of d ∼ 500 nm, which correlates very well with the structure confirmed by transmission electron microscopy. In particular, below the transition thickness, the formation of the high density grain boundary leads to the reduction in the μHall/μopt ratio as well as Nopt. As a result, we find that the thickness dependence of the carrier transport properties is almost completely governed by the grain boundary formation. On the other hand, when the ZnO layer is exposed to wet air at 85 °C, μHall reduces drastically with a minor variation of μopt due to the enhanced grain boundary scattering. We have also characterized textured ZnO:Al layers prepared by HCl wet etching by SE. The analysis revealed that the near-surface carrier concentration increases slightly after the etching. We demonstrate that the SE technique can be applied to distinguish various rough textured structures (size ∼ 1 μm) of the ZnO layers prepared by the HCl etching.