Abstract The concept of acidity in confined spaces is up to date poorly understood; especially, in case of media violating electroneutrality. Here, we describe the acidity of charged droplets via their ability to protonate simple nitrogen bases and we propose ways to modify the protonation efficiency with the help of additives. We observed that the protonation of compounds in charged water droplets is independent of solution‐phase acidity; instead, it can be adjusted with the help of additive type. On the other hand, the extent of protonation in charged methanol droplets can be adjusted with the conventional approach of changing the pH.