Low-temperature synthetic pathways can result in crystallization of metastable materials. These methods have been widely explored for the preparation of metal oxides. Adaptation of nonhydrolytic sol-gel chemistry to non-oxide systems offers an elegant route to transition-metal sulfides. The method can be exploited for the facile and reproducible synthesis of iron sulfide crystallizing in the troilite structure. This phase is only found in meteorites and planets and has previously been obtained by high-temperature or high-energy ball-milling methods. "Nonhydrolytic" sol-gel processing results in direct crystallization of troilite with no need for further calcination.