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The scintillation properties of Rb2LiCeCl6, a new scintillation material of the elpasolite family, are presented. Under X-ray excitation, broad emission band between 350 to 401 nm wavelengths is obtained. Such emission is attributed to cerium ion. The energy resolution of 662-keV photopeak measured with Rb2LiCeCl6 crystal is found to be 7.9% (FWHM). A maximum light yield of ~ 23 100 ph/MeV is measured. Under γ-ray excitation, Rb2LiCeCl6 single crystal showed two exponential decay time components. Comparison of X-ray excited emission and pulse height spectra of Rb2LiCeCl6 and Rb2LICeBr6 are also presented. Non-proportionality and energy resolution as a function of γ-rays energies are presented. This material is highly hygroscopic.