Phase-field crystal methodology is applied, for the first time, to study the effect of alloy composition on the clustering behavior of a quenched/aged supersaturated ternary Al alloy system. An analysis of the work of formation is adapted from a methodology developed in Fallah et al. to describe the dislocation-mediated nucleation and growth mechanisms of early clusters in binary alloys [Phys Rev B 2012;86:134112]. Consistent with the experiments, we demonstrate that the addition of Mg to an Al–1.1Cu alloy increases the nucleation rate of clusters in the quenched/aged state by increasing the effective driving force for nucleation, enhancing the dislocation stress relaxation and decreasing the surface energy associated with the Cu-rich co-clusters of Cu–Mg. Furthermore, we show that it is thermodynamically favorable for small subcritical clusters to have higher affinity for Mg than larger post-critical Cu-rich clusters, particularly depicting a two-stage clustering phenomenon.