Distribution of Ce in orthophosphate Sr3(PO4)2

•Distribution of Ce in Sr3 (PO4 )2 was studied by the combined XRD and XAFS analysis.•Single-crystal XRD confirms the location of Ce and vacancy or coexisting Li.•Ce K-edge EXAFS analysis supports the residence of Ce3+ at the 3a-site. The distribution of Ce in orthophosphate Sr3(PO4)2 was investigated by the combined single-crystal X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) analyses. Sr3(PO4)2:Ce3+ compounds with two different Sr sites (3a and 6c sites) were synthesized using the solid-state reaction method. Single-crystal XRD analysis confirmed the location of Ce at the 3a site along with the corresponding vacancy or coexisting Li at the 6c site. Additionally, the Ce K-edge EXAFS analysis supported the occupancy of Ce3+ at the 3a site rather than at the 6c site.