In this study, structural and electronic properties of CoAl₂O₄ spinel are investigated for the first time by means of quantum chemical computational tools. Coupling supercell periodic calculations under the density functional theory formalism with a nonempirical quasi-harmonic Debye model, we examine the influence of temperature on the relative stability of several cation distributions of Co²⁺ and Al³⁺ over tetrahedral and octahedral interstices of the oxygen sublattice. Our simulations are able to reproduce the experimentally observed trend: (i) the normal spinel is calculated to be the stable structure at static and low-temperature conditions, and (ii) as the temperature increases, the preference of structures with Al³⁺ at tetrahedral sites (and Co²⁺ at octahedral sites) is found to progress following an asymptotic conduct. The effects of the cation distributions on geometrical variations of electronic and magnetic properties of CoAl₂O₄ can be interpreted as dominated by the local behavior of Co²⁺ at octahedral sites.