High phosphorus Ni-P coatings, both unreinforced and modified by the addition of alumina (Al 2O 3) and zirconia (ZrO 2) nanoparticles, were manufactured by electroless deposition technique and heat-treated with different temperature and duration schedules. The effect of dehydrogenation (200 °C for 2 h) and its combination with crystallization heat treatment was studied in terms of microstructural changes and wear resistance. The amorphous structure of the coatings was not altered by the introduction of both Al 2O 3 and ZrO 2 nanoparticles, and the addition of 1.5 g/L of ZrO 2 yielded the highest microhardness due to better particles dispersion. Dehydrogenation improved hardness because of the early stages of grain growth; however, the greatest improvement in hardness (+120% compared to unreinforced Ni-P) was obtained after annealing at 400 °C for 1 h, because of the microprecipitation of the Ni 3P crystalline phase induced by thermal treatment. No detectable differences in hardness and microstructure were detected when annealing at 400 °C for 1 h with or without prior dehydrogenation; however, the dehydrogenated coatings exhibited a lower Young’s modulus. ZrO 2-reinforced coatings demonstrated improved wear resistance, and wear tests revealed that dehydrogenation is fundamental for lowering the coefficient of friction (−14%) and wear rate (−97%) when performed before annealing at 400 °C for 1 h. The analysis of the wear tracks showed that the non-dehydrogenated samples failed by complete coating delamination from the substrate, with abrasion identified as the predominant wear mechanism. Conversely, the dehydrogenated samples demonstrated better resistance due to the formation of a protective oxide layer, leading to an overall increase in the coating wear resistance. Abstract High phosphorus Ni-P coatings, both unreinforced and modified by the addition of alumina (Al 2O 3) and zirconia (ZrO 2) nanoparticles, were manufactured by electroless deposition technique and heat-treated with different temperature and duration schedules. The effect of dehydrogenation (200 °C for 2 h) and its combination with crystallization heat treatment was studied in terms of microstructural changes and wear resistance. The amorphous structure of the coatings was not altered by the introduction of both Al 2O 3 and ZrO 2 nanoparticles, and the addition of 1.5 g/L of ZrO 2 yielded the highest microhardness due to better particles dispersion. Dehydrogenation improved hardness because of the early stages of grain growth; however, the greatest improvement in hardness (+120% compared to unreinforced Ni-P) was obtained after annealing at 400 °C for 1 h, because of the microprecipitation of the Ni 3P crystalline phase induced by thermal treatment. No detectable differences in hardness and microstructure were detected when annealing at 400 °C for 1 h with or without prior dehydrogenation; however, the dehydrogenated coatings exhibited a lower Young’s modulus. ZrO 2-reinforced coatings demonstrated improved wear resistance, and wear tests revealed that dehydrogenation is fundamental for lowering the coefficient of friction (−14%) and wear rate (−97%) when performed before annealing at 400 °C for 1 h. The analysis of the wear tracks showed that the non-dehydrogenated samples failed by complete coating delamination from the substrate, with abrasion identified as the predominant wear mechanism. Conversely, the dehydrogenated samples demonstrated better resistance due to the formation of a protective oxide layer, leading to an overall increase in the coating wear resistance. Keywords: electroless Ni-P coatings; nanocomposite coatings; ZrO2 and Al2O3 nanoparticles; dehydrogenation; thermal treatments; instrumented indentation; wear resistance