The stability of ion irradiation induced defects and refractive index changes in LiNbO3, is examined in the temperature region 300 K ≦ TA ≦ 1370 K using the results of RBS, volume expansion, and reflection measurements. Due to the destruction of the crystal structure the activation energy of the Li2O‐diffusion in RBS‐amorphous layers is reduced to (0.62 ±; 0.07) eV. Thereby at temperatures TA > 700 K a mixed phase of LiNbO3 and LiNb3O8, can be formed. The restoration of the LiNbO3 crystal structure takes place in connection with the equalization of the Li2O‐concentration by diffusion from the substrate into the layer during annealing at TA = 1370 K.