Different long-chain primary alkylamines such as octylamine, dodecylamine, tetradecylamine, hexadecylamine or octadecylamine were used to stabilize Ni-NiO nanoparticles (metal:stabilizer ratio of 1:10) by an organometallic method in organic medium to evaluate their effect on the microstructural and magnetic properties. The Ni-NiO stabilized nanoparticles were characterized by Fourier transformed infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), conventional transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and dynamic light scattering (DLS). The results indicated an adequate stabilization of Ni nanoparticles with the different primary alkylamines. The semi-quantitative analysis suggests that Ni surface composition is a combination of the metallic state with NiO, NiOOH and NiO, but the chain length modified the content and proportion of these compounds. The highest Ni metallic state (57.2 at. %) was obtained with tetradecylamine as stabilizer. The morphology of the samples is similar to a core–shell semi-spherical, but the particle size tends to reduce with the alkyl chain length of primary amines from 20 to 8 nm. The saturation magnetization (Ms) showed important variations depending on the surface composition, for which variable particle size and Ni metallic content were determining factors for the magnetic response. [ABSTRACT FROM AUTHOR]