Electrodeposition of NiOOH is an attracting route toward nanosized films of NiO, a p-type semiconductor used in many advanced applications. In this paper, the deposition mechanism is thoroughly investigated aiming at the clarification of the deposition dynamics and the chemical nature of the deposit. We focused on initial stages of the potentiostatic deposition on ITO, which yields a nanostructured film. In the potential range investigated the process is mass transport controlled and strongly overlaps with oxygen evolution reaction. The nucleation regime, which is finely tunable, correlates with the surface extension of the film. Supporting electrolytes are found to suppress the deposition, likely by modifying the nickel speciation in the aqueous electrolyte. Further, through XPS investigation we shed light on the mixed gamma-beta NiOOH nature of the deposited film and its electrochemistry. This work provides precious understanding for future exploitations of anodic electrodeposited NiO, especially in applications where a strict control on surface morphology and thickness at the nanoscale level is mandatory. (C) 2019 Elsevier Ltd. All rights reserved.