A comprehensive temperature characterization method based on the GaNE2-high Raman mode and sapphire ruby R fluorescence lines from Raman spectra was developed to analyse the thermal distribution and heat transfer process of high-power flip-chip InGaN/GaN LEDs (FC LEDs). Our analysis demonstrated that in addition to the known problem that the edges of mesa were always the hottest point of FC LEDs, which was due to the current crowding effect, a noteworthy temperature difference was first observed between the sapphire substrate and n-GaN when the injection current was above 300 mA. A 'heat reservoir' was suggested to occur at the interface between the sapphire and n-GaN due to poor thermal conductivity of sapphire when a large amount of heat from the hottest spot cannot be effectively transferred to the Si mount via the active region under high injection currents.