We report on the photovoltaic properties of inverted polymer solar cells where the transparent electron-collecting electrode is formed by a ZnO-modified indium−tin oxide (ITO) electrode. The ZnO layers were deposited by atomic layer deposition (ALD) with varying thicknesses from 0.1 to 100 nm. The work function, surface roughness, and morphology of ITO/ZnO were found to be independent of the ZnO thickness. However, the device performance was found to be strongly dependent on a critical ZnO thickness, around 10 nm. Below the critical thickness the device performance was degraded because of the appearance of a “kink” in the current−voltage characteristics. The kink features became less pronounced after ultraviolet (UV) exposure. This was attributed to oxygen desorption, leading to an increased conductivity of the ZnO layer. At and above this critical thickness, the device performance significantly improved and no longer depended strongly on the thickness of the ZnO layer, in agreement with optical simulatio...