We synthesized a new tetraphenylethylene-modified chitosan bioconjugate,CS-TPE, that shows the aggregation-induced emission effect. It can self-assemble into fluorescent polymeric nanoparticles in an aqueous solution at pH 5.3 either alone or with the water-soluble bowl-shaped six-fold carboxylated tribenzotriquinacene derivativeTBTQ-C6via host–guest binding. The spherical nanoparticles formed byCS-TPEamphiphiles orTBTQ-C6/CS-TPEsupra-amphiphiles disintegrated under alkaline stimulation at pH 10.4 and the dispersion of the aggregates after the collapse in the presence ofTBTQ-C6was greatly improved. In addition, the fluorescence ofCS-TPEwas significantly enhanced by introducingTBTQ-C6, and remained relatively stable with variations in pH for bothCS-TPEandTBTQ-C6/CS-TPE. Such pH-responsive supramolecular spherical nanoparticles with stable fluorescence emission based onCS-TPEorTBTQ-C6/CS-TPEmay find applications in various fields, including the development of visual oral drug delivery systems.