AbstractNovel PVC membrane electrodes for the determination of betaine ion based on the formation of betaine‐tetraphenylborate (Be‐TPB) and betaine‐phosphotungstate (Be‐PT) ion‐exchangers as electroactive materials are described. The sensors show a fast, stable, near Nernstian response for 6.92 × 10‐6 to 7.94 × 10‐3 M and 1.0 × 10‐4 to 1.0 × 10‐2 M betaine hydrochloride (Be.Cl) in case of Be‐TPB electrode applying batch and flow injection analysis (FIA), respectively, and 2.95 × 10‐5 to 2.26 × 10‐3 M and 3.16 × 10‐5 to 1.0 × 10‐2 M in case of Be‐PT electrode for batch and FIA electrodes, respectively, at 25 °C over the pH range of 3.5‐10 with a cationic slope of 60.2 and 59.1 mV decade‐1 and a fast potential response of ≤ 15 s. The lower detection limits are 7.94 × 10‐6 and 3.18 × 10‐5 M Be.Cl for Be‐TPB and Be‐PT electrodes, respectively. Selectivity coefficient data for some common inorganic cations, sugars, amino acids and the components other than betaine, of the mixed drug investigated show negligible interference. The electrodes have been applied to the direct potentiometric determination of betaine hydrochloride in water and in a pharmaceutical preparation under batch and FIA conditions. Potentiometric titrations of Be.Cl with NaTPB and PTA as titrants were monitored with the developed betaine electrodes as an end point indicator electrode. The determination of Be.Cl shows an average recovery of 100.8 % with mean relative standard deviation of 0.61 %. The effect of temperature on the electrodes was also studied.