An excellent persistent luminescence (PersL) phosphor NaCa2GeO4F:Mn2+,Yb3+ has been synthesized by traditional solid-state reaction. By controlling the occupation sites of Mn2+ emitters, the PersL color of this phosphor can be optionally tuned in the red to green-yellow region, and the maximum spectral shift is more than 50 nm. Significantly, the red PersL can be measured for approximately 13 and 3 h (0.32 mcd/m(2)) and can be observed for more than 20 and 5 h with dark-adapted vision after exposure to ultraviolet irradiation and artificial sunlight, respectively. The crystal/electronic structure and photoluminescence/PersL properties of this phosphor have been investigated in detail. A series of the excitation temperature-dependent thermoluminescence experiments and the initial rising method have been conducted to study the trap properties of this phosphor. It reveals the reasons for the variation of PersL color, excellent red PersL, and degradation of green-yellow PersL. According to the results, the as-prepared NaCa2GeO4F:Mn2+,Yb3+ can be considered as an excellent red PersL phosphor, and it also has potential for application in optical storage.