This paper reports the molecular design and click syntheses of novel shape amphiphiles with molecular architectures beyond conventional giant surfactants. They include (1) the giant bolaform surfactant which consists of a polystyrene (PS) chain tethered with one hydrophilic POSS cage at each end of the chain (DPOSS–PS–DPOSS); (2) the giant gemini surfactant which contains two hydrophilic POSS cages and two PS tails tethered at one junction point (2DPOSS–2PS); and (3) the multi-headed giant surfactant which is composed of three hydrophilic POSS cages tethered at one end of a PS chain (3DPOSS–PS). The syntheses were achieved in a modular and efficient fashion following the sequential click approach in good yields, providing easy access to a family of shape amphiphiles with precise chemical structures and fine-tuned interactions for a systematic study of structure–property relationships.