The first report of a "molybdenum bronze" was by Alfred Stavenhagen and E. Engels in 1895.  They reported that electrolysis of molten  and  gave indigo-blue needles with metallic sheen, which they analysed by weight as . The first unambiguous synthesis of alkali molybdenum bronzes was reported only in 1964, by Wold and others.  They obtained two potassium bronzes, "red"  and "blue" , by electrolysis of molten + at 550 °C and 560 °C, respectively.  Sodium bronzes were also obtained by the same method. It was observed that at a slightly higher temperature (about 575 °C and above) only  is obtained.
Another preparation technique involves crystallization from the melt in a temperature gradient.  This report also called attention to the marked anisotropic resistivity of the purple lithium bronze  and its metal-to-insulator transition at about 24 K.
Hydrogen bronzes  were obtained in 1950 by Glemser and Lutz, by ambient-temperature reactions. The hydrogen in these compounds can be replaced by alkali metals by treatment with solutions of the corresponding halides.  Reactions are conducted in an autoclave at about 160 °C.