We demonstrate that the work function of Al-doped ZnO (AZO) can be tuned externally by applying an electric field. Our experimental investigations using Kelvin probe force microscopy show that by applying a positive or negative tip bias, the work function of AZO film can be enhanced or reduced, which corroborates well with the observed charge transport using conductive atomic force microscopy. These findings are further confirmed by calculations based on first-principles theory. Tuning the work function of AZO by applying an external electric field is not only important to control the charge transport across it, but also to design an Ohmic contact for advanced functional devices.