To measure and compare the intraoral pH and temperature of individuals during sleep with and without mouth breathing. Ten healthy participants [mean age = 25·8 (± 4·3)] wore a custom‐made appliance fitted with a pH probe and thermocouple for two sets of 48 h. Continuous pH and temperature measurements were taken from the palatal aspect of the upper central incisors. To simulate mouth breathing during sleep, participants wore a nose clip for two nights of the four, with the first group (n = 5) wearing the nose clip during the first night and the rest (n = 5) wearing the nose clip during the second night of sleep to balance any potential bias from the wearing sequence. Both qualitative and quantitative analyses were conducted. The mean intraoral pH during daytime was 7·3 (± 0·4) and during sleep was 7·0 (± 0·5). The mean intraoral pH during sleep with mouth breathing was 6·6 (± 0·5), which was statistically significant compared with the normal sleep condition (P < 0·01). The intraoral pH decreased slowly over the hours of sleep in all participants. When sleeping with forced mouth breathing, intraoral pH showed a greater fall over a longer period of time. The mean intraoral temperature was 33·1 °C (± 5·2) during daytime and 33·3 °C (± 6·1) during sleep, with no statistical significance between sleep with and without mouth breathing (P > 0·05). The results suggest that mouth breathing during sleep is related to a decrease in intraoral pH compared with normal breathing during sleep, and this has been proposed as a causal factor for dental erosion and caries.