Herein, the structural, optical and thermoluminescence properties of Cr doped Zn2TiO4 are explored extensively for a possible application in bioimaging. All the samples show prominent luminescence at wavelengths 712 and 716 nm, which correspond to Cr R and N2-lines, respectively. These R and N2 lines correspond to the presence of Cr3+ in undistorted and distorted sites. The excitation spectra of all the samples possess at least five different bands at 616, 440, 388, 330 and 283 nm. The persistent luminescence is observed upon excitation at all these wavelengths, suggesting the existence of both localized and delocalized mechanisms. The charges can be easily stored in deeper traps (trap depth > 1.0 eV) upon localized excitation with green and red light sources. However, upon excitation at wavelengths 254 and 365 nm, these traps were found empty when thermoluminescence glow curves were recorded immediately after excitation. Furthermore, it was observed that the trapping in these deeper traps through the delocalized band is possible when a delay in the thermoluminescence measurement is pursued. We attribute the possible reason for such delayed tunneling to the higher probability of retrapping than the recombination process.