In this work, the mesophase properties were tuned via mixing two discotic molecules with structural complementarity. Compared with the liquid crystalline hexakis(n-hexyloxy)triphenylene(H6TP)materials(columnar hexagonal phase from 53 8C to 91 8C), mesophase types as well as phase transition temperatures varied with the introduction of crystalline hexaazatriphenylene derivative(PBH)molecules. The introduction of less than 33% amount of PBH disrupted the columnar hexagonal phase formed by H6 TP remarkably, followed by the decreased clearing temperatures of liquid crystals. As the PBH amount was further increased, the destroyed columnar hexagonal phase was turned into the columnar rectangular phase, in which H6 TP and PBH molecules together formed the columnar mesophase. The formation of new mesophase contributed to the enlarged mesophase temperature(from44 8C to 144 8C). We speculated that the alkyl chains interaction induced by the PBH component competed with the strong p–p stacking between H6 TP molecules, thus altering the liquid crystalline properties including mesophase types and phase transition temperatures. Compared with the liquid crystalline hexakis (n-hexyloxy) triphenylene (H6TP) materials (columnar hexagonal phase 538C to 91 8C), mesophase types as well as phase transition temperature varied with the introduction of crystalline hexaazatriphenylene derivative (PBH) molecules. The introduction of less than 33% amount of PBH disrupted the columnar hexagonal phase formed by H6 TP remarkably, followed by the decreased clearing temperatures of liquid crystals. As the The formation of new mesophase contributed to the enlarged mesophase temperature (from 44 8C to 144 8C) We speculated that the alkyl chains interaction induced by the PBH component competed with the strong p-p stacking b etween H6 TP molecules, thus altering the liquid crystalline properties including mesophase types and phase transition temperatures.