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The coincidence site lattice (CSL) concept is often used in microstructural characterization by researchers studying grain boundary engineering as a method for improving the performance of polycrystalline materials. It is assumed that a high degree of shared lattice sites in the boundary between two grains will result in improved mechanical properties. For practical application of the CSL concept to experimental results, a maximum deviation from ideal CSL orientation relationships must be defined to distinguish potential CSL boundaries from random boundaries that are not likely to exhibit “special” properties. Several different maximum deviation criteria have been proposed in the literature. In this study, four of these criteria are investigated for their effectiveness in predicting the creep cavitation resistance of boundaries of different CSL character in three model alloys: pure Cu, Cu-Bi, and Cu-Sb. Bi and Sb strongly segregate to Cu grain boundaries and are detrimental to creep life. The experimental observations are compared to simulation results for a non-textured polycrystal. It is observed that only boundaries related to cubic annealing twins (Σ3 and Σ9) exhibit special resistance to creep cavitation, that boundaries with Σ > 3 are affected by the presence of segregants, and that the fraction of non-Σ(3,9) boundaries tracks closely with what would be expected from a random polycrystal. It is shown that more restrictive criteria result in more reliable characterization of the fraction of cavitation-resistant boundaries only because they exclude more non-Σ(3,9) boundaries from the analysis.