We report on structural characterization of sapphire photomodified by voids of sub-wavelength diameter surrounded by amorphised regions formed after exposure by tightly-focused femtosecond laser pulses of 800 nm wavelength and 150 fs duration at the single and double-pulse irradiation inside crystalline sapphire. Regrowth of a crystalline phase near the edge between the amorphous and crystalline phases was observed by transmission electron microscopy (TEM) in the case of double-pulse-irradiated locations. Regions patterned by single-pulse-induced voids inside sapphire were characterized by synchrotron X-ray diffraction (XRD) technique. The XRD patterns indicate presence of an expanded phase of the host crystal. The origin of structural changes observed in TEM and XRD is discussed and is consistent with fast thermal quenching.