The effects of heat waves (HW) are more pronounced in urban areas than in rural areas due to the additive effect of the urban heat island (UHI) phenomenon. However, the synergies between UHI and HW are still an open scientific question and have only been quantified for a few metropolitan cities. In the current study, we explore the synergies between UHI and HW in Seoul city. We consider summertime data from two non-consecutive years (i.e., 2012 and 2016) and ten automatic weather stations. Our results show that UHI is more intense during HW periods than non-heat wave (NHW) periods (i.e., normal summer background conditions), with a maximum UHI difference of 3.30°C and 4.50°C, between HW and NHW periods, in 2012 and 2016 respectively. Our results also show substantial variations in the synergies between UHI and HW due to land use characteristics and synoptic weather conditions; the synergies were relatively more intense in densely built areas and under low wind speed conditions. Our results contribute to our understanding of thermal risks posed by HW in urban areas and, subsequently, the health risks on urban populations. Moreover, they are of significant importance to emergency relief providers as a resource allocation guideline, for instance, regarding which areas and time of the day to prioritize during HW periods in Seoul.