Two neutral copper(I) halide complexes ([Cu(BTU)2X],X= Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU,N-(3,4-diheptyloxybenzoyl)-N′-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI–MS, elemental analysis, IR, and NMR spectroscopies (1H and13C), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH…X moieties (X= halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 × 10−7S·cm−1was achieved at 430 K for the chloro-complex and 1.37 × 10−6S·cm−1at 440K for the related bromo-complex.