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We devised a new method of determining the temperatures of materials with their electron-energy distributions. The Fermi–Dirac distribution convoluted with a linear combination of Gaussian and Lorentzian distributions was fitted to the photoelectron spectrum measured for the Au(110) single-crystal surface at liquid N2-cooled temperature. The fitting successfully determined the surface-local thermodynamic temperature and the energy resolution simultaneously from the photoelectron spectrum, without any preliminary results of other measurements. The determined thermodynamic temperature was 99 ± 2.1 K, which was in good agreement with the reference temperature of 98.5 ± 0.5 K measured using a silicon diode sensor attached to the sample holder. [ABSTRACT FROM AUTHOR]