Controlling the composition and phase formation of bulk and nanoscale solids underpins efforts to control physical properties. Here, we introduce a powerful new chemical pathway that facilitates composition-tunable synthesis, post-synthesis purification, and precise phase targeting in metal chalcogenide systems. When metal selenides and sulfides react with trioctylphosphine (TOP) at temperatures that range from 65 to 270 degrees C, selenium and sulfur are selectively extracted to produce the most metal-rich chalcogenide that is stable in a particular binary system. This general approach is demonstrated for SnSe2, FeS2, NiSe2, and CoSe2, which convert to SnSe, FeS, Ni3Se2, and Co9Se8, respectively. In-depth studies of the Fe-Se system highlight the precise phase targeting and purification that is achievable, with PbO-type Fe-Se (the most metal-rich stable Fe-Se phase) forming exclusively when other Fe-Se phases, including mixtures, react with TOP. This chemistry also represents a new template-based nanoparticle "conversion chemistry" reaction, transforming hollow NiSe2 nanospheres into hollow NiSe nanospheres with morphological retention.