This paper describes the synthesis and characterization of liquid crystals based on loop-shaped cationic copper(I) complexes of a multidentate ligand. Their synthesis involves the one-pot reaction of an alkyloxy-decorated pyridine-aldehyde unit with a diamine (2,2'-(ethylenedioxy)bis(ethylamine)) spacer to form in situ a pyridine-imine quadridentate-N4-donor ligand, L, which is able to chelate a copper(I) center associated with various noncoordinating anions. All of these compounds were characterized by NMR, IR, and electronic absorption spectroscopy, and more particularly by X-ray diffraction and mass spectroscopy, enabling unambiguous assignment of the [ML]+ mononuclear nature of the cationic components. The presence of six flexible alkyloxy chains at each end of the ligand associated with the rigidity of the core complex causes induction of a liquid crystal state with a columnar self-organized architecture, where the columns are packed in a hexagonal two-dimensional network.