The glass/air interface shows electrical properties that are unexpected for a widely used electrical insulator. The mobility of interfacial charge carriers under 80% relative humidity (RH) is 4.81 × 10-5 m2 s-1 V-1, 3 orders of magnitude higher than the electrophoretic mobility of simple ions in water and less than 2 orders of magnitude lower than the electron mobility in copper metal. This allows the glass/air interface to reach the same potential as a biased contacting metal quickly. The interfacial surface resistance R increases by more than 5 orders of magnitude when the RH decreases from 80 to 2%, following an S-shaped curve with small hysteresis. Moreover, the biased surfaces store charge, as shown by Kelvin potential measurements. Applying an electric field parallel to the surface produces RH-dependent results: under low humidity, the interface behaves as expected for an ideal two-dimensional parallel-plate capacitor, while under high RH, it acquires and maintains excess negative charge, which is lost under low RH. The glass surface morphology and potential distribution change on the glass/air interface under high RH and applied potential, including the extensive elimination of nonglass contaminating particles and potential levelling. All these surprising results are explained by using a protonic-charge-transfer mechanism: mobile protons dissociated from silanol groups migrate rapidly along a field-oriented adsorbed water layer, while the matrix-bound silicate anions remain immobile. Glass may thus be classified as the ionic analogue of a topological insulator but based on structural features and charge-transfer mechanisms different from the chalcogenides that have been receiving great attention in the literature.