Progress on separating the long-lived fission products has notably implied basic research on specific host matrices, especially for the immobilization of cesium. Barium hollandite (BaAl2Ti6O16) ceramics have received considerable interest because of their high cesium incorporation ability and chemical stability. This study deals with the preparation of hollandite in the BaxCsy(Al,Fe)2x+yTi8–2x-yO16 (x+y<2) compositional range by an oxide route. Different parameters such as the grain size of the precursor or the temperature and duration of sintering were changed in order to optimize ceramics synthesis. To estimate the hollandite radiation resistance, external electron irradiation experiments (simulating the β particles emitted by radioactive cesium) were performed on hollandite of simple composition. The irradiation-induced defects were studied by Electron Paramagnetic Resonance (EPR) spectroscopy and their nature is discussed.