This paper reports on the preparation and characterization of stable poly(vinyl alcohol) (PVA)-based dry hollow microparticles, readily convertible to gas-filled microballoons (MBs) in water suspension. The rehydrated MBs can be used as ultrasound contrast agents and for targeted drug delivery, while the dry MBs are suitable for encapsulation of biologically active gases. The MBs powder material is obtained by freeze-drying the as-prepared telechelic PVA-shelled MBs aqueous dispersion. The microstructure of the lyophilized MBs as well as of the starting and the reconstituted MBs in water suspension was examined using transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission X-ray microspectroscopy (STXM) and confocal laser scanning microscopy (CLSM). STXM observations below and above the oxygen K-edge reveal that 80% of the MBs originating from the lyophilized particles are gas-filled. Moreover, local carbon K near-edge X-ray absorption fine structure spectroscopy (NEXAFS) measurements evidenced that the chemical composition of the polymeric shell is preserved during the freeze-drying process and subsequent shelf storage for at least more than one year.