The separation selectivity of inorganic anions in capillary zone electrophoresis with reversed electroosmotic flow was altered by incorporating ≤7.5% v/v butan-1-ol in a chromate-based background electrolyte (BGE). Pronounced selectivity changes occurred for lipophilic anions, whereas, for the common inorganic anions, the changes were minor. The likely causes for these selectivity changes are discussed. Furthermore, BGEs with butan-1-ol yielded separations with (i) short times for lipophilic anions, (ii) smoother baselines, (iii) better resolutions, (iv) increased peak heights for iodide and thiocyanate, and (v) good reproducibility (≤4% RSD, n = 11) for absolute migration time, peak area, and peak height.