D-A　hybrid　heterostructures　are　an　emerging　class　of　crystalline　hybrid　materials　composed　of　semiconductive　inorganic　donors　and　organic　acceptors.　However,　due　to　the　steric　effects　of　the　inorganic　coordination　sites,　it　is　difficult　for　the　large　organic　molecules　to　form　compact　packing　at　the　molecular　level,　resulting　in　the　poor　efficiency　of　photoinduced　charge　transfers.　To　achieve　an　effective　carrier　separation　and　transfer,　herein　we　incorporated　third　donors　into　a　copper(i)　halide/thiazolo[5,4-d]　thiazole　D-A　heterostructure　to　construct　three　novel　three-component　complexes　(Me2-Py2TTz)Cu4I6·(I2)　(1),　(Me2-Py2TTz)Cu3I5·(pyrene)　(2)　and　(Me2-Py2TTz)Cu3I5·(perylene)　(3)　(Py2TTz　=　2,5-bis(4-pyridyl)　thiazolo[5,4-d]　thiazole),　respectively.　Due　to　the　spatial　distances　as　well　as　the　orbital　energies　between　the　copper(i)　halide　and　thiazolo[5,4-d]　thiazole　units　bridged　by　third　donors,　they　are　excellent　three-component　charge-transfer　complexes　(CTCs)　with　enhanced　electrical　properties.　©　The　Royal　Society　of　Chemistry　2021.