In many cases, limitations in conventional synthesis routes hamper the accessibility to materials with properties that have been predicted by theory. For instance, metastable compounds with local non-equilibrium structures can hardly be accessed by solid-state preparation techniques often requiring high synthesis temperatures. Also other ways of preparation lead to the thermodynamically stable rather than metastable products. Fortunately, such hurdles can be overcome by mechanochemical synthesis. Mechanical treatment of two or three starting materials in high-energy ball mills enables the synthesis of not only new, metastable compounds but also of nanocrystalline materials with unusual or enhanced properties such as ion transport. In this short review we report about local structures and ion transport of oxides and fluorides mechanochemically prepared by high-energy ball-milling.