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Eu3+ singly-doped Ba 2 La 6 Y 2 (SiO 4) 6 O 2 phosphors with hexagonal structure have been synthesized by the high-temperature solid-state reaction method. The crystal structure of the samples was analyzed. To investigate the site occupation of Eu3+ in Ba 2 La 6 Y 2 (SiO 4) 6 O 2 , the photoluminescence behavior of the phosphor was studied systematically. The emission spectra under specific wavelength excitations and the excitation spectra by monitoring emissions at 5D 0 →7F 0 transition wavelengths indicated that Eu3+ ions have entered two distinct sites in the compound. According to the concentration-dependent photoluminescence properties, the preferential site occupation was illustrated. In addition, the temperature-dependent PL measurement results revealed the high thermal stability of the sample and its application potential as a noninvasive optical thermometer. This work may help to provide an alternative approach to study the site occupation of Eu3+ ions in other functional materials. • A new Eu3+-activated Ba 2 La 6 Y 2 (SiO 4) 6 O 2 phosphor was synthesized via solid-state method. • The site occupation of Eu3+ was investigated according to the photoluminescence properties. • The phosphor has a high thermal stability. • The synthesized sample could have application potential as a noninvasive optical thermometer. [ABSTRACT FROM AUTHOR]