The surface of Li:Al nanolayers that were deposited by thermal evaporation of Li:Al alloy sources has been measured by ultraviolet photoelectron spectroscopy, which exhibited huge variation with the Li:Al nanolayer thickness. The hybrid organic light‐emitting devices with the controlled Li:Al nanolayer surface contacts as an electron‐injecting layer showed linearly varied charge transport and turn‐on voltages with the work function of the nanolayer surfaces.