A series of whitlockite-type AgCa10(PO4)7:RE3+ (RE = Sm, Dy) phosphors were successfully prepared via a high-temperature solid-state reaction method. The phase purity, photoluminescent properties, and thermal stability have been discussed in detail. Under 404 nm excitation, AgCa10(PO4)(7):Sm3+ exhibits red emission (604 nm) corresponding to the (4)G(5/2) -> H-6(7/2) transition. Under 352 nm excitation, AgCa10(PO4)(7):Dy3+ exhibits two emission peaks at 480 and 574 nm correspond to the F-4(9/2) -> H-6(15/2) and F-4(9/2) -> H-6(13/2) transition, respectively. The optimal AgCa10(PO4)(7):Sm3+ and AgCa10(PO4)(7):Dy3+ phosphors show good thermal stability. When the heating temperature reached 423 K, the relative intensity remains 90% and 86% compared to the luminescence intensity at room temperature of 298 K, respectively. Therefore, the above results indicate AgCa10(PO4)(7):RE3+ (RE = Sm, Dy) phosphors have potential applications in LEDs and display devices.