Samples with a target composition of Al62.5Cu25Fe12.5 (at.%) have been produced from the repeated cold rolling and folding (R&F) process of Al, Cu and Fe elemental foils. Upon early increments of the R&F cycle, the mechanically-induced process led to the fragmentation of the initial foils, which resulted in the dispersion of elemental Fe layers through the refined Al and Cu layers. After 40 R&F cycles the Al2Cu phase was detected, while Fe did not contribute to the formation of compounds. Thermal analyses suggested that the formation and dissolution of the Al2Cu and Al7Cu2Fe phases are critical steps for the synthesis of the i-phase during post-R&F treatment. Annealing between 650° and 750°C enabled the formation of the stable i-phase and resulted in high values of the microhardness.