A novel route for the synthesis of complex metal sulfides using hydrothermal coupled dissolution−reprecipitation reactions is reported. Two thiospinels, (Ni,Fe)
3S
4 (violarite) and Co
3S
4 (linnaeite), were synthesized using (Fe,Ni)
9S
8 (
pentlandite) and Co
9S
8 (cobalt
pentlandite) as precursors. The Fe/Ni ratio of (Ni,Fe)
3S
4 can be adjusted by varying the reaction conditions, for example, temperature (125–145 °C), pH (2.90, 3.90, 5.00), and precursor stoichiometry ((Fe
xNi
1−x)
9S
8,
x = 0.4, 0.5, 0.55, 0.6). Pure (Ni,Fe)
3S
4 can be synthesized by utilizing a flow-through hydrothermal cell rather than a static hydrothermal cell as the fluid flow improves mass transfer and flushes away the Fe
2O
3 byproduct from the reaction front. Synthesis times range from 10 to 20 days, compared to the traditional dry synthesis route for (Ni,Fe)
3S
4 that requires 3 months annealing to obtain a product of only 72
3 wt % purity. This synthesis route is ideal for preparing compounds with low thermal stabilities (<500 °C).