The effect of the complex ligature with nickel and REM (Ce, La) aluminides on the structure formation, the nature of the distribution of the elements, and the microhardness of the structural constituents of Al-5 wt.% Cu aluminum alloy were investigated. On the example of microalloying of the Al-5 wt.% Cu alloy with a master alloy containing Ni and REM (Ce, La) aluminides it was shown that a redistribution of Al and Cu occurs in α-solid solution and eutectic. This is reflected in the refinement of α-solid solution and eutectic at 0.15 wt.% of the master alloy addition and, accordingly, increases the microhardness of α-solid solution by 100 MPa and eutectic by 125 MPa.