Thermal comfort plays an influential role in the learning process. This paper explores the thermal comfort of students studying in a large university library in Johannesburg, South Africa. Quantitatively, Humidex was used to quantify and classify the level of thermal comfort using eight thermal data loggers that were installed in the library on the 1st of September 2023 and ran until the 25th of May 2024. These high spatiotemporal resolution meteorological data were used to calculate Humidex values for each 15 min interval, classifying periods of thermal discomfort from these output scores through the austral summer. Qualitatively, students’ self-reported thermal comfort in the library was explored through a questionnaire. The first floor was perceived to be the coolest and the third floor the warmest. Of the total respondents who consumed water, 8.33% felt hot and 1.96% felt very hot. The majority of respondents on the second floor added clothing in response to feeling cold or very cold; the third floor was characterised by the most respondents removing clothing in response to feeling hot or very hot; the first floor had minimal thermal behavioural adaption. This study shows that there is a risk of heat stress, especially if people do not have access to water.