The combined effects of global warming and increasing urban heat islands (UHIs) on air temperature and heat stress in cities are notable physical and mental health implications for citizens. With research having shown the effective role of urban green spaces in decreasing urban heat, this study investigated the cooling effect of a large urban park on thermal comfort outside the park area, from psychological and physiological perspectives. The studied park is located in the center of Madrid and adjacent to UHI. The study was performed by conducting field measurements and a survey with questionnaires. The measurements made on six summer days (with two-week intervals) showed that the park’s cooling effect could decrease the air temperature by 2.4-2.8°C right up to the edge of the heat island (600m), and decrease the physiological equivalent temperature (PET) by about 3.9°C. By decreasing air temperature and PET, this park was also shown to increase the perceived thermal comfort (PTC) of the citizens from the psychological perspective in the defined area of effect. This perceived thermal comfort was found to have a significant inverse relationship with PET (P-value <0.05). The examination of cognitive maps drawn by citizens showed that out of the 145 respondents, 68.3% marked the park as the area that they perceive as having the greatest thermal comfort, and prefer as the place to spend time enjoying thermal comfort, irrespective of its distance from their location.