In this work, we show that the synthesis of AlCuFe nanoparticles can be achieved by a wet ball-milling process. The AlCuFe intermetallic system is highly sensitive to the environmental embrittlement mechanism. Taking advantage of this, the wet ball-milling was used to increase the rate of grinding and accelerate the characteristic cleavage fracture of these phases. This research was carried out by subjecting Al 64 Cu 24 Fe 12 pre-alloyed ribbons to high-energy ball-milling under different powder–humidity relationships. The pre-alloyed and milled powders were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and scanning transmission electron microscopy (STEM). High resolution electron microscopy (HREM) measurements and energy-dispersive X-ray spectroscopy (EDXS) elemental chemical mapping confirm that the nanoparticles have a BCC structure with Al–Cu–Fe chemical composition. During the wet ball-milling, the aluminum content in the ψ-phase diminishes due to embrittlement mechanism which provokes its aperiodic disarrangement. This aluminum loss could be related with a ψ–β transformation.