“…Recently, a new type of giant amphiphiles that comprise “molecular nanoparticles (MNPs)” have been reported. − MNPs, such as polyhedral oligomeric silsesquioxanes (POSS), fullerene (C 60 ), or polyoxometalates (POM), have well-defined molecular structures, specific symmetry, and good shape and volume persistence, and act as hydrophobic, hydrophilic, or both parts of the giant amphiphiles. − Compared with traditional amphiphilic polymers, these giant amphiphiles show different interfacial behaviors due to their rigid conformation and less entanglement. , The platform of the Langmuir–Blodgett (LB) film provides effective tools to investigate the interfacial assembly of amphiphilic molecules. − Our previous work found that LB films of giant amphiphiles, containing a hydrophobic fluorinated MNP head and a poly(ethylene oxide) (PEO) tail, will show a fractal growth pattern if the PEO segment is long enough. , The LB film of the amphiphilic block copolymer PS- b -PEO does not show the fractal growth pattern despite containing a long PEO segment. − …”