In this study, synchrotron-based x-ray absorption microspectroscopy (μ-XAS) is applied to identify the chemical states of copper-rich clusters within a variety of silicon materials, including as-grown cast multicrystalline silicon solar cell material with high oxygen concentration and other silicon materials with varying degrees of oxygen concentration and copper contamination pathways. In all samples, copper silicide (Cu3Si) is the only phase of copper identified. It is noted from thermodynamic considerations that unlike certain metal species, copper tends to form a silicide and not an oxidized compound because of the strong silicon–oxygen bonding energy; consequently the likelihood of encountering an oxidized copper particle in silicon is small, in agreement with experimental data. In light of these results, the effectiveness of aluminum gettering for the removal of copper from bulk silicon is quantified via x-ray fluorescence microscopy, and a segregation coefficient is determined from experimental data to be at least (1–2)×103. Additionally, μ-XAS data directly demonstrate that the segregation mechanism of Cu in Al is the higher solubility of Cu in the liquid phase. In light of these results, possible limitations for the complete removal of Cu from bulk mc-Si are discussed.