A　1-D　hybrid　copper(I)　halides,　[(phen)Cu3I3]n(phen　=　1,10-phenanthroline)(1)　with　novel　D6R　(double　six-membered　rings)　Cu6I6　cores,　was　synthesized　by　solvothermal　reaction　and　characterized　by　single-crystal　X-ray　diffraction.　In　1,　nitrogen　atoms　from　phen　replace　two　I　of　CuI4　tetrahedron　to　give　distorted　tetrahedral　geometries　(CuI2N2),　then　CuI2N2　tetrahedron　shares　corners　via　μ3-I　to　generate　an　extended　1-D　zigzag　chain.　Two　zigzag　chains　combines　with　one　1-D　(Cu4I4)n　chain　containing　D6R　cores　via　μ3-I-Cu　(from　cores)　bonds　to　form　the　infinite　1-D　ribbonlike　polymer　along　the　a-axis.　Furthermore,　the　title　compound　is　stabilized　by　conspicuous　C-H···I　hydrogen　bonds,　π-π　and　d10-d10　metallic　interactions.　Experimental　and　theoretical　optical　property　investigation　indicates　that　1　possesses　semiconductor　property.　DFT　calculation　was　executed　to　probe　the　electronic　structure　of　1.　To　our　interest,　phen　act　as　a　property　control　species　with　its　π*　electrons　appear　in　the　forbidden　band.　©　Springer　Science+Business　Media,　LLC　2009.