Long-persistent luminescence (LPL) materials have attracted intensive attention due to their fascinating emission after excitation. However, current LPL materials typically depend on external doping to introduce traps or emitting centers, resulting in a complex synthesis and controllability. For the first time, we develop another category of undoped LPL materials based on antimonate CaSb 2 O 6 , which exhibits blue LPL for over 8000 s. Both experimental and theoretical evidence indicate that excitons are trapped by intrinsic oxygen vacancies. Then, they are detrapped and recombine through singlet and triplet emission of Sb 3+ to form LPL. Moreover, CaSb 2 O 6 maintains approximately 100% of its initial LPL performance and structural integrity even after being treated under 1000 °C, UV irradiation, and extreme conditions (pH = 1 or 13). This study highlights the significant potential of antimonates as robust and versatile luminescent materials.