Ion-selective electrode determinations of potassium and calcium have been carried out on skim milk powder and the results compared with data obtained by flame emission spectroscopy for potassium and by atomic absorption spectroscopy for calcium. The data indicate that ion-selective electrodes can be used as an alternative to spectroscopic methods for determining these metals by using a dry-ashing pretreatment procedure. Acid digestion pretreatment is not recommended because of the ensuing high ionic strength and possible interferences. Sodium and magnesium contents obtained by spectroscopy are also quoted for interest. The various percentage metal contents are: potassium: 1.96 ± 0.155 (ISE direct) 1.81 ± 0.144 (ISE Gran) and 1.82 ± 0.076 (flame emission), sodium: 0.511 ± 0.017 (flame emission), calcium: 1.37 ± 0.095 (ISE direct), 1.36 + 0.079 (ISE Gran) and 1.41 ± 0.082 (flame aas), and magnesium 0.119 ± 0.003 (flame aas).