A series of naphthalene-substituted triphenylene liquid crystals (LCs), viz. triphenylene-2,3,6,7,10,11-hexayl hexakis(6-alkenyloxy-2-naphthoate)s (HTPnN compounds) were synthesized and characterized. Alkenyloxy groups containing three to eleven carbon atoms were used as peripheral spacers in these liquid crystals. The discotic liquid crystals synthesized trap one to three water molecules depending on the length of their peripheral spacers. Differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction measurements confirm both nematic (Nd) and rectangular disordered columnar (Colrd) phases for most of the synthesized discotic LCs. The clearing temperatures of these discotic LCs increase with increasing peripheral spacer length. A hybrid aligned HTP9N sample was investigated to evaluate its optical performance. Retardation values of this hybrid sample decrease with increasing wavelength and increase with increasing measuring angle.