Over the past few years, several studies have been conducted on the development of Al-Si-Cu-Mg alloys for PBF-LB/M processing. The attention gained by these systems can be attributed to their light weight and strength provided by a solid solution in the as-built state and by precipitation after heat treatment. However, published studies have kept the copper content below its solubility limit in the Al-Cu binary system under equilibrium conditions (5.65 wt%). The present study aims to explore Al-Si-Cu-Mg systems with high copper content, starting with the well-known AlSi10Cu4Mg system, moving towards AlSi10Cu8Mg, and arriving at AlCu20Si10Mg, a system never before processed with PBF-LB/M. Through the SST approach, the production of bulk samples, advanced microstructural characterization by SEM and FESEM analysis, phase identification by XRD analysis, and preliminary investigation of the mechanical properties through Vickers micro indentations, the effects of copper quantities on the processability, microstructural properties, and mechanical behavior of these compositions were investigated. The obtained results demonstrated the benefits of the supersaturated solid solution and the fine precipitation resulting from the addition of high Cu contents. In particular, the AlCu20Si10Mg system showed a very distinctive microstructure and unprecedented microhardness values.