Microstructural features of nanostructured copper-matrix composites produced via high-energy milling were studied. Copper–graphite–alumina batches were planetary ball milled up to 16 h; copper–graphite batches were also prepared under the same conditions to evaluate the effect of contamination from the milling media. The microstructure of the produced materials was characterized by field emission gun scanning electron microscopy/energy-dispersive spectroscopy and related to Raman, X-ray diffraction, and particle size analysis results. Results showed that alumina was present in all milled powders. However, size reduction was effective at shorter times in the copper–graphite–alumina system. In both cases the produced powders were nanostructured, containing graphite and alumina nanoparticles homogeneously distributed in the copper matrix, especially for longer milling times and in the presence of added alumina. Copper crystallite size was significantly affected above 4 h milling; nanographite size decreased and incipient amorphization occurred. A minimum size of 15 nm was obtained for the copper crystallite copper–alumina–graphite composite powders, corresponding to 16 h of milling. Contamination from the media became more significant above 8 h. Results suggest that efficient dispersion and bonding of graphite and alumina nanoparticles in the copper matrix is achieved, envisioning high conductivity, high strength, and thermal stability.