This volume includes papers presented at the second International Workshop on "Oxide-based Systems at the Crossroads of Chemistry," held at Villa Olmo in Como, Italy, 8-11 October. The selected papers present the highlights of recent research in the field of oxide structure. A wide range of oxidic materials, including real oxides, zeolites and layer-structured systems, is considered and described in terms of preparation methods, structural characterization and the relation between active sites, structure and catalytic properties. The application of the most powerful simulation and physical-chemical techniques show their usefulness in discovering and explaining structural and dynamic properties of complex materials. Moreover the development of sophisticated spectroscopical and analytical techniques are shown to significantly improve the growth of surface oxide science, generating new tools for the knowledge of catalyst structure and reaction mechanisms. An interesting feature is the inclusion of papers which show the mutual roles of experiment and theoretical models.