In　this　study,　we　report　a　unique　solution-combustion　synthesis　of　Mn4+　doped　CaYAlO4　microcrystals　and　demonstrate　a　narrow-band　deep-red　emission.　Through　the　simulation　of　low-temperature　photoluminescence　(PL)　spectroscopy　and　theoretical　fitting　on　temperature-dependent　PL　intensity　at　T　4,　it　is　found　that　luminescence　thermal　quenching　effect　was　mainly　attributed　to　four-dominant　phonon　interaction　with　Mn4+　electronic　states.　More　interestingly,　the　deviation　of　luminescence　decay　curve　from　the　single-exponential　mode　at　T　＞　400　K　suggests　that　the　occurrence　of　two　radiative　transitions　is　a　consequence　of　ionically　thermal　excitation　to　the　second　excited　state　of　4T2.　These　findings　provide　not　only　a　general　approach　to　identify　the　predominant　phonon　vibration,　but　also　deep　insights　into　the　effect　of　weak　electron-phonon　coupling　on　PL　properties　of　solid-state　luminescent.　©　2022　Elsevier　B.V.