Large-scale growth of low-cost, efficient, and durable non-noble metal-based electrocatalysts for water splitting is crucial for future renewable energy systems. Atomic layer deposition (ALD) provides a promising route for depositing uniform thin coatings of electrocatalysts, which are useful in many technologies, including the splitting of water. In this communication, we report the growth of a NiO/Ni catalyst directly on carbon fiber paper by atomic layer deposition and report subsequent reduction and oxidation annealing treatments. The 10–20 nm NiO/Ni nanoparticle catalysts can reach a current density of 10 mA·cm−2 at an overpotential of 189 mV for hydrogen evolution reactions and 257 mV for oxygen evolution reactions with high stability. We further successfully achieved a water splitting current density of 10 mA·cm−2 at 1.78 V using a typical NiO/Ni coated carbon fiber paper two-electrode setup. The results suggest that nanoparticulate NiO/Ni is an active, stable, and noble-metal-free electrocatalyst, which facilitates a method for future water splitting applications.