The synthesis and liquid crystalline properties of new dimers with triphenylene donor (D) core tethered via a flexible spacer to a monofunctionalized anthraquinone acceptor (A) core, D-A, are reported. These dimers have hydroxyl (D-A(OH)) or acetyloxy (D-A(OAc)) functional group. The linear trimers, D-A-D, are also reported here. The chemical structures of these dimers and trimers are characterized by spectroscopic and spectrometric analysis. The liquid crystalline properties are investigated by polarizing optical microscope (POM) and differential scanning calorimetry (DSC). The dimers D-A(OH) having the spacer length similar to peripheral alkoxy chains exhibit the nematic (N) phase, whereas dimers D-A(OH) and D-A(OAc) having longer spacer length compared with peripheral alkoxy chains exhibit the columnar (Col) phase. The trimers exhibit N or Col mesophases, as confirmed by X-ray diffraction (XRD) studies, according to the similar rule as in D-A. Thus the spacer length and functional group have more influence on molecular self-assembly to exhibit the liquid crystalline properties. It is noted that some of these dimers and trimers show N or Col phase at room temperature. To the best of our knowledge, this is the first for molecules with non-branched but normal peripheral chains.