Commercial AlSi7Mg alloy represents the usual choice for complex geometry casting production. The market imperative to improve mechanical properties imposed the design of new chemical composition of AlSi7MgCu alloy with high content of Cu (up to 1.435 wt.%). This represents a challenge in order to achieve advanced properties. The interaction of a number of alloying (Si, Mg, Cu) and trace elements (Fe, Mn) influenced a wide range of complex reactions occurring and therefore leading to intermetallic phase precipitation. The characterization of novel chemical composition interaction and its solidification sequence was achieved by modelling an equilibrium phase diagram, simultaneously performing both thermal analysis and metallographic investigations. Copper influence was indicated in the whole solidification process starting with infiltration in modified Chinese script phase Al15(Fe,Mn,Cu)3Si2, beside common intermetallic Al5FeSi. Copper addition encourages formation of compact complex intermetallic phases Al5Cu2Mg8Si6 and Al8(Fe,Mn,Cu)Mg3Si6. Solidification ended with secondary eutectic αAl + Al2Cu + βSi. Microstructure investigation allows volume reconstruction of the microstructure and distribution of particular phases. Chemical compositions enriched in copper content and developed microstructural constituent through solidification sequence of AlSi7MgCu alloy contribute to a significant increase in mechanical properties already in an as-cast state.