Diffusion-like behavior of excitons within europium doped vanadate phosphors is studied, with emphasis on the trapping potential induced by Eu3+ and VO43− luminescence. We describe the hopping, energy transfer, and decay of excitons by means of a continuous-time Markov chain distinguished by a local and delocalized trapping potential. Our model compares luminescence from decay of excitons with the trapping problem, where VO43− traps are present everywhere, while Eu3+ ions are placed randomly. We distinguish two types of trapping potentials induced by europium traps. In the localized model, simplify the lattice to Zd where the trapping potential of europium traps is only present at randomized sites in the lattice. By applying the large deviation principle for the occupation times measure, as done by Donsker and Varadhan previously, we find probability mass asymptotics of the form exp td/(d+2). For a simulation-like approach, we describe the delocalized model, where exciton movement and trapping in crystal lattices of Rb3LuV2O8:Eu3+ and YVO4:Eu3+ and is modeled using parameters such as temperature, migration rates, emission lifetimes, and europium concentration to estimate luminescent properties of the materials. Experimental data from vanadate lifetimes of Rb3LuV2O8:Eu3+ and VO43− /Eu3+ emission ratio’s of YVO4:Eu3+ are compared to the model, which agree relatively well within the confidence of the model. For YVO4:Eu3+, we have found an activation energy of Ea = (101 ± 4) meV. We discuss how our simplified model can be extended to incorporate thermal and concentration quenching, and how to account for defects in the lattice. While we discuss our findings for europium doped vanadate phosphors, the results we have found are applicable for a range of other luminescent materials.