To prevent casein adsorption and improve between-run repeatability, a CE procedure is developed for cation analysis in milk using a modified imidazole/alpha-hydroxyisobutyric acid (HIBA) BGE system to operate at pH 6 to match the pH of milk and elevate imidazole concentration to enhance its buffer action. The procedure is shown to produce a fast, economic and efficient method for cation separation in milk with only simple dilution. Upon direct hydrodynamic injection of diluted milk sample at 8 cm for 30 s in an uncoated column with a BGE consisting of 10 mM imidazole, 10 mM HIBA and 10% methanol at pH 6.0 under +18 kV, baseline separation was achieved for K+, Na+, Ca2+, Mg2+, Mn2+, Cd2+, Co2+, Ni2+ and Zn2+. Agreeable results at 95% confidence level were obtained using CE and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for milk samples after protein removal. Baseline-resolved peaks for essential minerals were obtained for fresh and non-refrigerated reconstituted milks. Long-term stability was demonstrated by repeated determinations without rinsing and improvement in repeatability was shown by rinsing with 60 mM SDS in BGE. Information on metal speciation useful for nutritional assessment was obtained from CE to complement the ICP methods.