A defined surface hydration of the glass electrode is secured by pre-treatment with 0.1 N HF followed by rinsing with pure 0.1 N HCl for a few minutes. On subsequent contact with 0.1 N HCl containing HF, the electrode potential shows a change which is determined by the [HF]. The immediate reaction is an adsorption of HF by the glass surface. This is followed, at [HF] higher than 0.01 N, by the substitution of two F− for OH− per Si atom. With increasing HF the attack on the Si-O-Si bonds becomes severe, but it can be tolerated to a considerable degree because the newly formed surface is identical with the previous one. Some applications of the glass electrode in titrations with HF are suggested in an appendix.