Li-doped NiO epitaxial films with high electrical conductivity and atomically flat stepped surfaces were fabricated by a combined technique of pulsed laser deposition and subsequent annealing. It was determined that subsequently annealing at temperatures as low as 600 °C significantly decreased electrical conductivity due to Li evaporation when the film surface was not protected from Li evaporation. To suppress Li evaporation, a yttria-stabilized-zironia plate was used to cover the film surface, which raised the annealing temperature up to 1300 °C while maintaining a high Li concentration and electrical conductivity. Thermally annealing at this temperature also improved crystal quality and formed epitaxial films with atomically flat stepped surfaces. The films were single crystalline at least in observation areas, 10 μm × 10 μm. A reasonably large Hall mobility approximately 0.05 cm2/Vs similar to that reported for bulk single-crystal NiO and a visible-light transmission in excess of 75% were obtained on 120-nm-thick films. Although annealing at higher temperatures such as 1400 °C can further improve the structural and optical properties, the Li concentration in the films was decreased to <3% of the as-deposited film.