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The control of humidity between certain limits is essential to avoid the alteration of historical objects, such as unstable historical glasses. However, the usual limits can be altered due to the presence of volatile organic compounds. This work presents the results of the exposure of soda, potash, and mixed‐alkali silicate glasses to neutral and acidic (formic) atmospheres with ∼30%, ∼70%, and ∼100% relative humidity. The hygroscopic capacity of the glass was analyzed by gravimetry, and the surface alteration was evaluated by infrared spectroscopy, optical microscopy, and ion chromatography. In all glasses, the alteration begins with alkali ions' lixiviation followed by the silica network's hydrolytic attack. The results showed that soda and mixed‐alkali silicate glasses exhibit similar behavior, while the potash‐lime one experienced the fastest degradation due to its composition. Results also confirmed that high humidity increased the alteration rate causing a higher hygroscopicity and reactivity of glasses. Finally, acidic environments promoted the ion‐exchange reaction at high humidity, accelerating the lixiviation of alkaline ions and promoting the diffusion of water into the glass network. [ABSTRACT FROM AUTHOR]