The solid-phase epitaxial regrowth of Rb-irradiated α-quartz during annealing was investigated. The depth distribution of Rb atoms and the thickness of the amorphous layers calculated using Rutherford backscattering and Channeling (RBCS) spectrometry. It was observed that the chemically guided epitaxy in α-quartz demonstrated the correlations which governed the epitaxial regrowth, the Rb out-diffusion, and the oxygen exchange between the silica matrix and annealing gas. The results show that the swelling of the SiO2 matrix during implantation and recompaction during epitaxy was proven by the surface topography measurements.