Urban overheating (due to climate change and urbanization) and COVID-19 are two converging crises that must be addressed in tandem. Fine-scale, place-based, people-centric biometeorological and behavioral data are needed to implement context-specific preventative measures such as mask-wearing. This study collected local biometeorological measurements in diverse urban spaces (square, urban park, river quay) in Novi Sad, Serbia on hot sunny summer days (27–30 August 2020) during the COVID-19 pandemic. Observations were supplemented by an online survey asking questions about thermal sensation, comfort, and concurrent protective behavior of the local population. Biometeorological measurements show that the main square in the city center was the most thermally uncomfortable area. According to the survey, it was also perceived as the least safe space to not contract the virus. The urban park was perceived as the most thermally comfortable area in the morning and during midday. It was also considered the safest urban space for outdoor activities. In the evening, the river quay was the most thermally comfortable area in the city. Intra-urban differences in Physiologically Equivalent Temperatures were highest during midday, while differences in air temperatures were highest in the evening. More than 70% of the respondents did not wear face masks when it was hot because of breathing issues and feeling warmer than without mask. Most people wearing a mask felt “slightly warm” in the morning and evening, while the majority of respondents felt “hot” during midday. Only 3% of the respondents felt comfortable while wearing a mask, while 97% experienced some degree of discomfort (from slight discomfort to very uncomfortable). Our study shows that fine scale temporal and spatial urban biometeorological data and population surveys should be included in decision-making processes during the pandemic to develop climate-sensitive health services that are place-based, people-centric, and facilitate planning towards green, resilient, and inclusive cities.