Activator-free zinc aluminate (ZA) nanophosphor was synthesized through a sol-gel combustion route, which can be used both as a blue-emitting phosphor material and a white-emitting phosphor material, depending on the annealing temperature during synthesis. The material also has the potential to be used in optical thermometry. These fascinating color-tunable emission characteristics can be linked with the various defect centers present inside the matrix and their changes upon thermal annealing. Various defect centers, such as anionic vacancy, cationic vacancy, antisite defect, etc., create different electronic states inside the band gap, which are responsible for the multicolor emission. The color components are isolated from the complex emission spectra using time-resolved emission spectroscopy (TRES) study. Interestingly, the lifetime values of the various defect centers were found to change significantly from milliseconds to microseconds upon thermal annealing, which makes the phosphors more diverse (i.e., either long-persistent blue-emitting phosphors or short-persistent white-emitting phosphors). Fourier transform infrared (FTIR) and diffuse reflectance spectroscopy (DRS) confirmed the presence of antisite defect centers such as Al or Zn in the matrix. X-ray absorption fine structure (EXAFS) study showed that the spinel structure was more disordered in nature for low-temperature-annealed compounds. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies were also carried out in order to characterize various anionic and cationic vacancies and their clusters present in the compounds. Antisite defect centers such as Al or Zn, which act as an electron or hole trap, were found to be responsible for the diverse lifetime behavior. To gain insight about the electronic states inside the band gap, density functional theory (DFT)-based calculations were performed for both pure and various vacancy-introduced spinel structures. Finally, based on the theoretical and experimental results, for the first time, a detailed investigation of various defect-induced emission behavior in ZA is presented, which also explains the mechanism of color tunability and dynamic lifetimes.