We examined the influence of momentary annealing on the nanoscale surface morphology of NiO(111) epitaxial thin films deposited on atomically stepped sapphire (0001) substrates at room temperature in O2 at 1.3 × 10−3 and 1.3 × 10−6 Pa using a pulsed laser deposition (PLD) technique. The NiO films have atomically flat surfaces (RMS roughness: approximately 0.1–0.2 nm) reflecting the step-and-terrace structures of the substrates, regardless of the O2 deposition pressure. After rapid thermal annealing (RTA) of the NiO(111) epitaxial film deposited at 1.3 × 10−3 Pa O2, a periodic straight nanogroove array related to the atomic steps of the substrate was formed on the film surface for 60 s. In contrast, the fabrication of a transient state in the nanogroove array formation was achieved with RTA of less than 1 s. However, when the O2 atmosphere during PLD was 1.3 × 10−6 Pa, random crystal growth was observed and resulted in a disordered rough surface nanostructure after RTA.