Hydrothermal synthesis is the most important method in the wet chemical method, it was introduced to the process of tungsten bronze preparation in the early 1980s. Mix WO₃-W-LiOH as ratio of 1: 3: 2 in a certain amount of water, heated under 700 ℃ (constant pressure) for 9h to prepare purple crystal, proven as the hexagonal structure Li_0.30WO₃ with a = 0.740 5 nm and c = 0.755 4 nm. The early hydrothermal synthesis temperature is relatively high, and now it is reported that more low-temperature hydrothermal synthesis.

 

Kenneth P. Reis and A. Ramanan prepared tungsten bronze hexagonal structure by hydrothermal synthesis by acidified tungstate solution. Reaction in solution at T = 155 ℃, P = 5kPa for about 3 d, the control of pH value of duration is critical. The product synthesis unit cell parameters are a = 0.730 0 nm, c = 0.771 9 nm of hexahedral Li_xWO_{3 + x / 2}. Similar low-temperature hydrothermal synthesis, that several reactions in aqueous solution is directly heated, there are more reports about pressurized synthesis tungsten bronze crystals. As WO3, KOH and N2H4·H20 react at 360 ℃, prepare single crystal whiskers of K_0.4WO₃. Acidify WO₃, NaBH₄ (or KBH₄) with hydrochloric acid, prepare NaxWO₃ (or KxWO₃) sol at 350 ℃, and annealing by 600 ℃ and 850 ℃  to obtain crystals. Hydrothermal synthesis at low temperatures must solve the problem of the intensity of reducing selection, in order to ensure the portion W^{6 +} reduction, thereby generating tungsten bronze. Select acidification and use of organic synthesis are commonly-used means of strong reducing agent.

 

In wet chemical method, because of its relatively low synthesis temperature, the better product crystallized state becomes a hot research focus of synthesis method, but there are not many tungsten bronze kinds now synthesized by this method .