Upon excitation with extreme ultraviolet (EUV) radiation, optical windows CaF2 and sapphire emit strong photoluminescence (PL) in the ultraviolet region 200-400 nm. The spectral profiles of the windows observed in the PL spectra appear strongly dependent on their temperature. We suggest the use of PL spectra of CaF2 and sapphire excited with EUV light to indicate the temperature for EUV applications such as nano-photolithography technology in manufacturing semiconductor devices; potentially, the method is applicable to a wide range of radiation including the vacuum-ultraviolet (VUV) and EUV regions and in all fields.