Using the achiral 1,4-naphthalenedicarboxylic acid (H2L) ligand and corresponding cadmium(II) salts, under hydrothermal conditions, a novel 3D chiral inorganic-organic hybrid complex with the formula [Cd(μ6-L)(DMF)]n has been isolated and characterized by single-crystal X-ray diffraction, FT-IR, TGA, and luminescent analysis. The crystal crystallizes in the chiral space group P212121, a = 6.7180(10) Å, b = 13.507(2) Å, c = 15.229(2) Å, Z = 4, the flack parameter is near zero (–0.02(4)). Two kinds of 1D infinite right-handed Cd-O-Cd helical chains can be observed, which are further interlinked into 1D infinite Cd-O-Cd linkage in a unique arrangement way. Solid-state luminescent spectrum of 1 also has been investigated indicating the strong emission band centered at 494 nm upon excitation at 370 nm. The result also represents a good example of the construction of those chiral inorganic-organic hybrid frameworks containing infinite M-O-M linkage using the achiral precursor. Supplementary materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.