Microstructural features strongly affect magnetism in nano-granular magnetic materials. In the present work we have investigated the relationship between the magnetic properties and the self-organized microstructure formed in a Cu75–Ni20–Fe5 alloy comprising ferromagnetic elements and copper atoms. High resolution transmission electron microscopy (HRTEM) observations showed that on isothermal annealing at 873 K, nano-scale solute (Fe,Ni)-rich clusters initially formed with a random distribution in the Cu-rich matrix. Superconducting quantum interference device (SQUID) measurements revealed that these ultrafine solute clusters exhibited super-spinglass and superparamagnetic states. On further isothermal annealing the precipitates evolved to cubic or rectangular ferromagnetic particles and aligned along the 〈100〉 directions of the copper-rich matrix. Electron energy-band calculations based on the first-principle Korringa–Kohn–Rostocker (KKR) method were also implemented to investigate both the electronic structure and the magnetic properties of the alloy. Inputting compositions obtained experimentally by scanning transmission electron microscopy–electron dispersive X-ray spectroscopy (STEM–EDS) analysis, the KKR calculation confirmed that ferromagnetic precipitates (of moment 1.07μB per atom) formed after annealing for 2 × 104 min. Magneto-thermogravimetric (MTG) analysis determined with high sensitivity the Curie temperatures and magnetic susceptibility above room temperature of samples containing nano-scale ferromagnetic particles.