Capillary electrophoresis (CE) can very efficiently resolve different dissolved metal ion species as long as rates of ligand exchange are slow relative to time scales required for electromigration. Here, we detail the separation of several Cr^III and Co^III complexes with the multidentate chelating agents iminodiacetic acid, nitrilotriacetic acid, trans-1,2-cyclohexanediaminetetracetic acid, N-(2-hydroxyethyl)ethylenediaminetriacetic acid, trimethylenediaminetetraacetic acid, and ethylenediaminetetraacetic acid. Successes in speciating some Ni^II and Co^II complexes are also reported. For Cr^III and Co^III, subtle differences in metal ion-chelating agent stereochemistry, chelating agent denticity, and number of bridging ligands are discernible due to the high resolving power of CE. New peaks and heightened baselines were encountered when a pH buffer with strong complexing properties (orthophosphate) was employed in the background electrolyte. For this reason, we recommend using pH buffers with very weak or negligible complex properties (e.g., MES and MOPS).