Developing　a　yellow　phosphor　with　broadband　emission　covering　more　red-light　areas　is　an　effective　approach　to　achieve　high-quality　solid-state　lighting.　In　this　study,　a　novel　yellow-emitting　nitride　phosphor,　Ca5Si2Al2N8:Ce3+,　was　successfully　prepared　at　atmospheric　pressure　and　lower　temperatures　(1300°C),　and　its　structure-property　relation　was　revealed　using　crystal　refinement,　photoluminescence　(PL)　spectra,　time-resolved　PL　spectra,　and　density-functional　theory　calculations.　The　results　demonstrate　that　Ca　atoms　occupy　three　different　crystallographic　sites　in　the　lattice,　which　are　substituted　by　Ce3+　to　form　multiple　luminescence　centers.　Thus,　Ca5Si2Al2N8:Ce3+　emits　strong　yellow　light　with　a　maximum　peak　at　585 nm　and　a　wide　emission　band.　Compared　with　YAG:Ce3+,　Ca5Si2Al2N8:Ce3+　has　a　wider　emission　band　with　a　FWHM　of　150 nm,　which　can　effectively　cover　the　green　and　red　areas.　Moreover,　the　sample　can　be　fully　excited　by　a　blue　LED　chip　due　to　its　broad　excitation　band.　Notably,　the　Ca5Si2Al2N8＇s　tight　crystal　structure　composed　of　edge-sharing　AlN4　and　SiN4　tetrahedra　pairs　guarantee　its　thermochemical　stability　and　quantum　efficiency.　Furthermore,　Ca5Si2Al2N8:Ce3+　exhibits　better　thermal　stability　than　YAG:Ce3+.　The　results　indicate　that　Ca5Si2Al2N8:Ce3+　is　a　promising　yellow　phosphor　for　WLEDs.　©　2021　The　American　Ceramic　Society