Steel molds used for aluminum die-casting often fail due to excessive wear or cracking phenomena associated with the soldering effect in contact with molten aluminum, which leads to the formation of iron-based intermetallic compounds and causes problems in the cast components. One solution is to apply protective coatings whose composition is less reactive with the molten aluminum and improve its hardness, toughness, wear, and corrosion resistance, thus prolonging its service life. This work evaluates the effectiveness of Ti-6Al-4V coatings deposited by twin wire arc spraying in an air or nitrogen atmosphere. Nitrogen was used as the carrier and shielding gas for the in-flight molten particles. Coatings were deposited by varying the stand-off distance, the nitrogen gas pressures, and the substrate temperature. The microstructure of the coatings is interlayered, one porous layer of dendrites and one highly densified layer. The presence of TiN, TiO2, α-Ti, and β-Ti phases was confirmed by different characterization methods. For instance, x-ray photoelectron spectroscopy measurements confirmed the presence of N-Ti, O-Ti, and N-O bonds, with the oxygen/nitrogen/titanium percentage associated with the formation of a non-stoichiometric (Ti, Al, V)NxOy phase. Finally, the reactivity of selected oxynitrided Ti-6Al-4V coating in contact with molten aluminum showed a low reaction rate compared to the coarse reaction layer suffered by the uncoated steel substrates.