The methods for preparation of highly transparent optical ceramics based on simple and complex fluoride compounds of elements of the first, second, and third Group in the Periodical system are considered. The use of precursors as nanopowders and processes of their self assembling on heating results in maximally homogeneous, transparent, and mechanically strong ceramics. The resulting calcium fluoride ceramics possess optical losses of 10 -2 -10 -3 cm -1 at 1.06 µm and shock resistance characterized by the fracture toughness К 1С = 4.7±0.3 MPa m 1/2 (for comparison, for a calcium fluoride single crystal К 1C = 1.5±0.15 MPa m 1/2 ). Regularities of the chemistry of fluoride nanopowders were considered in comparison with the oxide nanopowders: the fluorides are prone to hydrolysis, and powder nanoparticles precipitated from aqueous solutions have complex and heterogeneous (over the volume) chemical composi tion. The spectral luminescence properties of the ceramics activated by rare earth metals (Ce 3+ , Nd 3+ , Er 3+ , Yb 3+ ) or containing active color centers are presented. The generation properties of the lithium fluoride ceramics with the color centers and the ternary Ca-Sr-Yb fluoride during diode laser pumping are described.