The improvement of comfort monitoring resources is pivotal for a better understanding of personal perception in indoor and outdoor environments and thus developing personalized comfort models maximizing occupants’ well-being while minimizing energy consumption. Different daily routines and their relation to the thermal sensation remain a challenge in long-term monitoring campaigns. This paper presents a new methodology to investigate the correlation between individuals’ daily Thermal Sensation Vote (TSV) and environmental exposure. Participants engaged in the long-term campaign were instructed to answer a daily survey about thermal comfort perception and wore a device continuously monitoring temperature and relative humidity in their surroundings. Normalized daily profiles of monitored variables and calculated heat index were clustered to identify common exposure profiles for each participant. The correlation between each cluster and expressed TSV was evaluated through the Kendall tau-b test. Most of the significant correlations were related to the heat index profiles, i.e., 49% of cases, suggesting that a more detailed description of physical boundaries better approximates expressed comfort. This research represents the first step towards personalized comfort models accounting for individual long-term environmental exposure. A longer campaign involving more participants should be organized in future studies, involving also physiological variables for energy-saving purposes.