Using the combustion method, red emitting Sr4Al14O25:Eu3+, Sm3+ phosphors were synthesised. The properties of photoluminescence were also studied. Orange (591 nm) and red (614 nm) emissions from Sr4Al14O25:Eu3+ phosphor, with 394 nm being the most exciting. The dominant excitation line was around 404 nm and was attributed to 6H5/2→ 4F7/2, while the emission spectrum had emission peaks at 565 nm and 603 nm. Furthermore, the chromaticity coordinates of 6H5/2→ 4F7/2 phosphors were found in the red region (0.677, 0.322), (0.640, 0.359) by the Commission International de l'Eclairageth. According to the current findings, Sr4Al14O25:Eu3+, Sm3+ phosphors can be used as a red emitting phosphor in near-ultraviolet (n-UV) based w-LEDs.