This study examined the effect of mood states on students’ thermal sensations within a university library comprising quiet-study and group-study rooms. Through concurrent subjective and objective assessments over five consecutive workdays, this study investigated the influence of psychological factors, particularly mood states, in influencing thermal sensations. This study addressed a paucity of prior research in library settings where both independent and collaborative studies have been undertaken. Subjective data (i.e. personal information, thermal assessment and mood states) via questionnaires and objective data (i.e. air temperature, radiant temperature, relative humidity and air velocity) via on-site measurements were collected during five working days. Statistical analyses (ANOVA, t-test, correlations and regression) indicated that male students and those with bad feelings (e.g. hostile and upset) reported significantly higher thermal sensation votes (TSVs) ( p < 0.05) compared to females and those with neutral/good feelings (0.4–0.5 difference out of 7). Two predictive models for TSV were developed for males and females, considering factors like body mass index (BMI), operative temperature and mood states. This research offers insights for designing specific study environments to improve thermal comfort, fostering students’ well-being and guiding future initiatives in this area.