The Donnan theory is extended to formulate a model for determination of the distribution coefficient of calcium in slurries of fully bleached and unbleached kraft fibers at different pH, taking into account the presence of both carboxylic and phenolic groups in the fibers. The intrinsic dissociation constants of the carboxylic acid groups and phenolic hydroxyl, which are the key inputs of the extended model, were determined by potentiometric titration. The extension improves the model prediction significantly, particularly when the presence of phenolic lignin in fibers becomes significant. However, when the pH exceeds 10, the model underestimates the distribution coefficient, suggesting that other factors may influence the fiber charge. The structural changes of the fiber wall at high pH and the presence of hydroxyl groups on the cellulose, which ionize at high pH, may be major factors.