Persistent luminescence is a singular property of some materials which are able to store the excitation or light irradiation energy at intrinsic traps or defects before slowly emitting lower energy photons within several hours. When such compounds are prepared as nanoparticles (NPs), when functionalization is realized to get colloidal materials well dispersed in aqueous medium, such nanoprobes open the use of the persistent luminescence for bioimaging applications. Recently, the numbers of in vivo applications increased with new modalities and new expectations. In this review, we focused our attention on the ZnGa2O4:Cr (ZGO:Cr) nanoparticles. When ZnGa2O4 (ZGO), a normal spinel is doped with Cr3+ ions, a high brightness persistent luminescence material with an emission spectrum perfectly matching the transparency window of living tissues is obtained. It allows in vivo mouse imaging with an excellent target-to-background ratio. One interesting characteristic of ZGO:Cr lies in the fact that its persistent luminescence can be excited with orange/red light, well below its band gap energy and in the transparency window of living tissues. This important property allows multiple re-excitations to perform long term bioimaging. Antisite defects of the direct spinel structure are assumed to provide shallow traps which store the excitation light. Charge release by room temperature thermal excitation and recombination center, here trivalent chromium, are responsible for the persistent luminescence. Following a primary excitation (UV or visible), one also observed that trapped charges can be released under 977nm light stimulation for several spinel gallate materials, therefore increasing the modalities and the materials envisioned for in vivo excitation of these NPs.