Temporally compound heatwaves (CHWs), two consecutive heatwaves (HWs) with an intermittent cool break between them, are projected to occur more frequently under a warming globe. However, their spatiotemporal characteristics and interaction with urban heat island (UHI) are unexplored at the continental scale. Using observational data from over 2000 ground-based stations over China, we find that CHWs constitute an increasing portion of HW hazard from 1961 to 2021. The increasing trend is especially evident when using the daily minimum temperature to define hot days, suggesting an aggravated thermal environment at night. Urban-rural contrast of CHW trends illustrates that urbanization contributes substantially to the increased frequency of CHWs in cities, especially in southern China. Results show that mean UHI intensity (UHII) tends to weaken under HW and CHW conditions, which correlates with increased pressure and reduced precipitation. During CHW events, UHII reduces during cool break due to enhanced evaporative cooling in urban areas under precipitation. The interaction between UHI and HW is subject to change with background climate, which is positive for dry regions and negative for wet regions. This study provides insights into CHW evolution over mainland China and demonstrates the need for heat mitigation strategies under climate change.