In this paper, we have examined analytical spectrometry using Eu Lγ4. The oxidation-state-fluctuating compound EuPd2Si2 exhibits the largest temperature-induced valence changes among all Eu systems and does not have a structural phase transition below 298 K; EuPd2Si2 has a precipitous valence transition near 150 K. Hence, high-resolution EuLγ4emission spectra of EuPd2Si2 at 298 K and 30 K were measured using a multicrystal multidetector spectrometer. The spectra exhibited substantial differences, thereby indicating that the spectral shapes of Eu Lγ4 emissions depend on the oxidation state of the Eu ions. We have also demonstrated the applicability of Eu Lγ4 emission to oxidation state selective extended X-ray absorption fine structure (EXAFS) spectroscopy through partial fluorescence yield measurements with an excitation energy range of approximately 0.5 keV. In this manner, we have addressed and resolved two key questions in analytical spectrometry using EuLγ4.