Developing new persistent luminescent phosphors, a unique class of inorganic materials that can produce a visible light emission lasting minutes to hours requires improving our understanding of their fundamental structure-property relationships. Research has shown that one of the most critical components governing persistent luminescence is the existence of lattice defects in a material. Specifically, vacancies and anti-site defects that coincide with substitution of the luminescent center, e.g., Eu2+ or Cr3+, are generally considered essential to generate the ultra-long luminescent lifetimes. This research solidifies the connection between defects and the remarkable optical properties. The persistent luminescent compound Zn(Ga1-xAlx)2O4 (x = 0-1), which adopts a spinel-type structure, is investigated by examining the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) at the Cr K and Zn K edges. This investigation reveals a structural distortion of the octahedrally coordinated main group metal site concurrent with increasing Al3+ content. Moreover, these results suggest there is a dependence between the local crystallographic distortions, the presence of defects, and a material's persistent luminescence. In combination, this work provides an avenue to understand the connection between the structure-defect-property relationships that govern the properties of many functional inorganic materials.