When the urban heat island (UHI) effect coincides with a heat wave (HW), thermal comfort conditions in cities are exacerbated. Understanding the surface energy balance (SEB) responses to HWs is critical for improving predictions of the synergies between UHIs and HWs. This study evaluates observed SEB characteristics in four cities (Beijing, Łódź, London and Swindon), along with their ambient meteorological conditions, for both HW and background summer climate (BC) scenarios. Using the Analytical Objective Hysteresis Model (AnOHM), particular emphasis is on the heat storage. The results demonstrate that in London and Swindon not only the amount of daytime heat storage but also its portion relative to the net all-wave radiation increase under HWs. Results further demonstrate that such increases are strongly tied to lower wind speeds. The effects of different UHI mitigation measures on heat storage are assessed using AnOHM. Results reveal that using reflective materials and maintaining higher soil moisture availability may offset the adverse effects of increased heat storage.