A new arylene ethynylene macrocycle (AEM) molecule bearing endo-acetamide groups was obtained by a Pd/Cu mediated homo-coupling reaction. Introducing tetraethylene glycol ether as a linkage between two C-shaped fragments substantially improved the final cyclization yield (30%). Concentration-dependent ¹HNMR experiments indicated that strong aggregates formed through H-bonds were observed for this new macrocycle with amide groups in solution. And also, this macrocycle was fluorescent in solution and showed a highly selective fluorescence quenching response toward the highly toxic Hg²⁺. More importantly, this macrocycle could induce gelation of several solvents. Significantly, an interesting aggregation-induced enhanced emission (AIEE) behavior was observed for this macrocycle upon gelation. Both SEM and TEM investigations revealed that nanoporous structures existed in the xerogels. This study offers a new molecular design approach to develop fluorescent gels from planar AEM molecules with a functional cavity.