The quest to develop thin-film solution processing approaches that offer low-cost and preferably low-temperature deposition, while simultaneously providing quality semiconductor characteristics, has become an important thrust within the materials community. While inorganic compounds offer the potential for outstanding electronic properties relative to organic systems, the very nature of these materials rendering them good electronic materials—namely strong covalent bonding—also leads to poor solubility. This review presents a “dimensional reduction” approach to improving the solubility of metal chalcogenide semiconductors, which generally involves breaking the extended framework up into discrete metal chalcogenide anions separated by small and volatile cationic species. The resulting soluble precursor may be solution-processed into thin-film form and thermally decomposed to yield the desired semiconductor. Several applications of this principle to the solution deposition of high-performance active layers for transistors (channel mobility >10 cm2 V−1 s−1), solar cells (power conversion efficiency of as high as 12%), and fundamental materials study will be presented using hydrazine as the deposition solvent.