Two members of the pyroxene family, the germanate-type LiFeGe2O6 and the titanate-type LiFeTi2O6, are prepared for the first time via non-conventional one-step mechanosynthesis. The evolution of the as-prepared materials in the course of mechanosynthesis and their structural state on the long-range and local atomic scales are characterized by X-ray diffraction and Fe-57 Mossbauer spectroscopy, respectively. Both, the nanocrystalline nature of LiFeGe2O6 and the nanoglassy state of LiFeTi2O6 are revealed.