The dispersion of electron-deficient ferrocenium ions was studied in the electron-rich media of two different triphenylene-based columnar hexagonal liquid-crystalline phases. These composites were characterized using polarizing optical micrography (POM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), visible absorption spectroscopy, and do and ac conductivity measurements. It was found that these composites form donor-acceptor systems that enhance the quasi-one-dimensional conductivity of the discotic system without altering the hexagonal columnar mesophase. The absorbance spectra confirm the formation of a charge-transfer complex between the electron-rich discotic molecules and the electron-deficient ferrocenium ions.