Hollow polyphosphazene microcapsules have been fabricated by the covalent layer‐by‐layer assembly of polydichlorophosphazene (PDCP) and hexamethylenediamine (HDA) on aminosilanized silica particles, followed by core removal in a HF/NH4F solution. The hollow and intact microcapsules in both wet and dry states have been characterized by transmission electron microscopy and confocal laser scanning microscopy. The chemical structure of the microcapsules has been verified by FT‐IR spectroscopy. The microcapsules could be hydrolytically degraded in a phosphate buffer at biological pH.
