In　recent　years,　organic-inorganic　hybrid　materials　have　demonstrated　exceptional　performance　in　nonlinear　optics,　attracting　widespread　attention.　However,　there　are　relatively　few　examples　of　coordination　compounds　synthesized　with　Cu　as　the　metal　center　that　exhibit　excellent　nonlinear　optical　properties.　In　this　study,　we　successfully　synthesized　a　pair　of　enantiomers　named　R/S-Cu2I2　by　reacting　chiral　ligands　with　CuI.　The　crystal　structure　reveals　a　one-dimensional　copper-iodide　chain　structure　built　by　Cu2I2　clusters,　and　its　ordered　arrangement　in　space　provides　not　only　a　strong　second　harmonic　generation　(SHG)　signal　(1.24　×　KDP)　but　also　a　large　birefringence　(0.15@1064　nm).　Under　excitation　at　395　nm,　the　crystals　exhibit　red　fluorescence　peaked　at　675　nm.　The　CD　spectra　of　R/S-Cu2I2　show　a　distinct　mirror-symmetric　Cotton　effect,　and　their　CPL　signals　are　corresponding　and　opposite　in　the　emission　range,　with　a　maximum　glum　of　approximately　±2.5　×　10−3.　Theoretical　calculations　using　density　functional　theory　were　also　carried　out　to　enhance　our　understanding　of　the　correlation　between　their　structures　and　optical　properties.　©　2024　The　Royal　Society　of　Chemistry.