We report a new platform for design of soluble precursors for CuInSe2 (CIS), Cu(In1-xGax)Se-2 (CIGS), and Cu2ZnSn(S,Se)(4) (CZTS) phases for thin-film potovoltaics. To form these complex phases, we used colloidal nanocrystals (NCs) with metal chalcogenide complexes (MCCs) as surface ligands. The MCC ligands both provided colloidal stability and represented essential components of target phase. To obtain soluble precursors for CuInSe2, we used Cu2-xSe NCs capped with In2Se42- MCC surface ligands or CuInSe2 NCs capped with {In2Cu2Se4S3}(3-) MCCs. A mixture of Cu2-xSe and ZnS NCs, both capped with Sn2S64- or Sn2Se64- ligands was used for solution deposition of CZTS films. Upon thermal annealing, the inorganic ligands reacted with NC cores forming well-crystallized pure ternary and quaternary phases. Solution-processed CIS and CZTS films featured large grain size and high phase purity, confirming the prospects of this approach for practical applications.