The transient part of the ion conductivity enhancement in CaF2/BaF2 heterolayers on annealing at elevated temperatures is investigated. It is well established that annealed heterolayers exhibit a strongly increased F− conductivity parallel to the interfaces and a substantial but less strong enhancement perpendicular to the interfaces [N. Sata et al., Nature 408, 946 (2000) and X. X. Guo et al., Appl. Phys. Lett. 91, 103102 (2007)]. This is explained by a F− redistribution from BaF2 to CaF2 as a consequence of contact equilibrium. As to the behavior during annealing, two remarkable features are observed: (i) freshly prepared films show an even higher conductance enhancement if measured in the parallel direction, which decreases on annealing toward the equilibrium situation, while (ii) in the perpendicular direction the conductance variation is very small and of opposite sign. On the basis of the conductivity experiments as a function of temperature, layer-thickness, and anisotropy, in combination with structural investigations by transmission electron microscopy, we conclude that in agreement with earlier experience on composite materials, a high density of unstable defects is formed close to the heterointerfaces during multilayer preparation, which heals off during the temper process. In the final contact equilibrium a regular array of misfit dislocations is left, enabling the epitaxial contact. By assuming that the electroactive unstable microstructural defects are arranged at the heterointerfaces and are charged by fluoride ion trapping, we can explain the experimental features including the space charge overlap using the combined Mott–Schottky and Gouy–Chapman models used previously. The results indicate that the charge density stays approximately constant during the annealing process.