Pillar[5]arene (P5A) mesogens were synthesized by decorating the central P5A core with ten benzylether dendron via click reaction. Each benzylether dendron was terminated with multialkoxy chains. Such P5A mesogens can self-assemble into liquid crystal (LC) phases with layer structure (Smectic A phase) and tubular structure (Colhex/p6mm phase). Molecular packing models for these mesophases were initially established. Additionally, such P5A mesogens can act as chemo-sensor to recognize Fe3+ and Cu2+. The influence of the number of terminal alkoxy chain on the self-assembly and chemo-sensor properties of these P5A derivatives were investigated.