A novel layered MOF, {[Pb(HBic)(HBic)Cl] · 2HO} ( I), was hydrothermally obtained by the reaction of PbCl with 1- H-benzimidazole-5-carboxylic acid (HBic) and fully characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR, TG-DTA, and luminescent spectra. Structural analysis suggests that complex I is a 2D layer assembled from helical Pb(II)-HBicchains and bridging chloride linkers, which is H-bonded together into a 3D supramolecular network. Additionally, I in the solid-state exhibits a favorable fluorescent emission at room temperature due to the intraligand charge transfer, suggesting its potential application as fluorescence materials. [ABSTRACT FROM AUTHOR]