A new type of composites, i.e. polymer-in-ceramic (as opposed to the “classical” ceramic-in-polymer approach) was introduced into the field of composite polymeric electrolytes. In this work the preparation of porous ceramic samples based on alumina is designed and their properties are characterised by XRD, porosimetry and SEM. Special setup was developed for the preparation of electrolytes in vacuum/controlled atmosphere conditions and it was used for preparing the composites. The studied systems exhibited excellent mechanical properties, high conductivities and good stability vs. Li metal electrodes under prolonged storage.