Copper in Si was shown to be strongly bound at cavities formed by He ion implantation and annealing. Evolution of this system during heating was observed by Rutherford backscattering spectrometry and transmission electron microscopy. Results were mathematically modeled to characterize quantitatively the binding of Cu in the cavities and, for comparison, in precipitates of the equilibrium silicide, &eegr;‐Cu3Si. Binding of Cu to cavities occurred by chemisorption on the walls, and the binding energy was determined to be 2.2±0.2 eV relative to solution in Si. The heat of solution from the silicide was found to be 1.7 eV, consistent with the published phase diagram. These findings suggest the use of cavities for metal‐impurity gettering in Si devices. Hydrogen in solution in equilibrium with external H2gas displaced Cu atoms from cavity walls, a mechanistically illuminating effect that is also of practical concern for gettering applications.