The construction of highly ordered nanostructure plays an important role in realizing the specific functions of organic materials. However, it remains challenging to design photoelectric materials with sub-10-nm nanostructures. Herein, a novel tetraphenylethylene derivative tethered with polyhedral oligosilsesquioxane nanocages (TPE-BPOSS) was designed and synthesized. The experimental results reveal that the introduction of POSS nanocages endows TPE-BPOSS with a hierarchically sub-10-nm ordered structure composed of columnar phase of non-planar TPE cores and crystalline phase of POSS moieties. Moreover, due to the transition between the ordered and disordered structure, TPE-BPOSS can exhibit reversible mechanochromism property. It is speculated that incorporating POSS nanocages into different non-planar fluorophores may be a new strategy to prepare functional materials with sub-10-nm nanostructure and luminescent property.