We describe an ion-based cavity-QED system in which the internal dynamics of an atom is coupled to the modes of an optical cavity by vacuum-stimulated Raman transitions. We observe Raman spectra for different excitation polarizations and find quantitative agreement with theoretical simulations. Residual motion of the ion introduces motional sidebands in the Raman spectrum and leads to ion delocalization. The system offers prospects for cavity-assisted resolved-sideband ground-state cooling and coherent manipulation of ions and photons.