Abstract The corrosion behavior of electrodeposited nickel-based coatings with W, Mo, and TiOx as potential catalytic material for hydrogen evolution reaction (HER) in highly aggressive media, 0.5 M H 2 SO 4 and 6 M KOH, is presented. A wide range of electrochemical and spectroscopic methods have been used, such as linear sweep voltammetry, open-circuit potential (OCP), electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS) to characterize the coatings before and after a residence time of 336 h in the model corrosion environment. The NiW alloy and the NiWTiOx composite coating demonstrate the best corrosion resistance in an acidic environment due to the stable tungstate phase formation (H 0.33 O 3 W and H 2 O 4 W) on the surface. In alkaline environments, all the systems studied show enviable resistance, but the alloys containing molybdenum stand out.