In this work, we reported a new series of multifunctional molecular columnar liquid crystalline phases with different terminal functional groups, MTM-1, MTM-2 and MTM-3. The macromolecule materials exhibited an ordered hexagonal columnar mesophase, high thermal stability, and excellent AIE properties in the THF-H2O system. Furthermore, it has been demonstrated that changing the terminal electronic affects the intermolecular forces and thus has a significant effect on the temperature range of the columnar mesophase. Specifically, the fluorescence quantum yield of MTM-1 in the solid state is as high as 45%. It is worth highlighting that the peripheral electron supply effect is favorable to enhance the fluorescence quantum yield. This work provides a new method for designing and synthesizing novel AIE liquid crystal materials.