Giant shape amphiphiles (GSA) are giant molecules made with nano-building blocks that have distinct shapes. The incompatible packing behaviors of the nano-building blocks of GSA could create cavities within certain conformers of the GSA, but the host-guest chemistry of GSA has not been explored yet. In this study, POSS-PDI-POSS (PPP), which is made by connecting two nano-cubes, isobutyl-polyhedral oligomeric silsesquioxanes (POSS), to a conjugated pi-conjugated core, perylene diimide (PDI), is demonstrated as a novel acyclic synthetic host. In its bent conformer, PPP shows a cavity next to its PDI core. Via forming host-guest complexes with pi-conjugated guests such as pyrene and perylene, PPP is found to transform from the bent-conformer into the extended-conformer, creating the steric features to accommodate guest molecules. Subsequent thermal annealing of the host-guest complexes removes the pi-conjugated guests and restores the bent conformation and photophysical properties of PPP, which verifies that PPP, as a novel acyclic host, is capable of dynamic host-guest assembly. Moreover, the results prove that cavities at the molecular level can be created by connecting nano-building blocks with distinct shapes. This finding may inspire developments in the host-guest chemistry of GSA and nanomaterial innovation.