In this paper, a novel kind of tristrontium sodium antimony(V) oxide (NaSr₃SbO₆:Mn⁴⁺; NSSO:Mn⁴⁺) material was developed, whose crystal structure is different from the well-researched Mn⁴⁺-doped antimoniate double pervoskite materials. The optimal NSSO:0.006Mn⁴⁺ can be mainly excited using ultraviolet/near-ultraviolet (UV/n-UV) and partial blue lights with a high quantum yield of 46% upon 365 nm UV excitation and good temperature dependent performance.