This study explores the thermal perceptions and comfort of residents and tourists at the Xi'an Ming Dynasty Ancient City Wall Scenic Area, addressing a gap in comparative outdoor thermal comfort studies in historical settings. Meteorological measurements and questionnaires collected between July 2019 and March 2021 analyze physical, individual, social, and psychological factors influencing thermal sensation, comfort, and acceptability across seasons. The RayMan model calculates Physiological Equivalent Temperature (PET), with data analyzed using SPSS 27.0. Results show Neutral PET (NPET) values of 17.1 °C for residents and 18.6 °C for tourists, and Preferred PET (PPET) values of 18.4 °C and 20.8 °C, respectively. Thermal Acceptability Ranges (TAR) are 13.5 °C–26.7 °C for residents and 15 °C–24.1 °C for tourists. Whether the measurement space contains water sources significantly affects temperature and humidity, while vegetation impacts wind speed. Physical factors predominantly affect perceptions, with individual factors becoming more important for tourists in winter. The findings provide insights for optimizing the thermal environment in scenic open spaces to enhance the comfort of both residents and tourists.