In this article, the electronic interaction of medium-energy ions with hafnium dioxide is studied. Stopping cross sections for He ions in the energy range from 30 to 160 keV have been measured in backscattering experiments from thin films of HfO 2 on Si using time-of-flight medium-energy ion scattering. The observed energy loss for helium ions is found to be high compared to expectations from earlier results for hydrogen in HfO 2 , a result which indicates a contribution from energy-loss processes that is different from direct excitation of electron-hole pairs in close collisions. Furthermore, data exhibit a significant deviation from velocity proportionality. A discussion of the results, together with data from studies for H and He in SiO 2 , show characteristic differences which are traced back to different electronic structures of the target materials and their influence on the charge-exchange channels that are active in the interaction with helium. Charge exchange, in turn, via shifted mean-charge states, will influence the observed ionization along the ion track. The results can furthermore serve as reference values for ion-beam-based depth profiling at medium and low ion energies.