The present paper described the determination of potassium and sodium ions with a liquid-phase diaphragm glow discharge emission spectroscopy (LDGD-AES) in aqueous solution. The discharge was formed in a pin hole on a dielectric diaphragm interposed between two submerged graphite electrodes. Effects of applied voltage and the addition of organic additive methanol on the determination were examined. It was found that increasing the applied voltage and adding of methanol can increase the detection sensitivity and decrease the detection limit. Limits of detection for K and Na were 0.007 and 0.001 mg·L-1 under the applied voltage of 850 V and addition of 0.6%～0.8% methanol, respectively. It was demonstrated that the LDGD-AES is a promising technique in measurements of metal ions in aqueous solution, because no optical interferences from the electrodes and the background molecular bands from air were found.