Pyrene derivatives (PCns) bearing four linear alkanoyloxy chains (n=7, 9, 11, 15) were synthesized and shown to exhibit mesophases as a result of forming charge-transfer (CT) complexes with strongly electron-accepting 2,4,5,7-tetranitro-9-fluorenone (TeNF). The mesomorphic properties were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and variable-temperature X-ray diffraction (XRD) studies. The discotic lamellar phase was confirmed by XRD measurements, but no indication of intercalation of TeNF was observed. The CT complexation was supported by not only spectroscopic studies but the thermal behavior of the co-ground mixture.