Multiblock motifs occur in proteins such as silk, elastin and ion channels. These motifs are advantageous to develop the characteristic mechanical properties through the formation of segregated intermolecular assemblies, and utilized to construct cylindrical channels in a membrane by folding and assembly with intra- or intermolecular interactions. As nature shows such elegant examples of multiblock molecules exerting sophisticated functions, synthetic multiblock molecules and copolymers have gained increasing attention as emerging structural motifs for realizing unique properties and functions. Recent notable examples of synthetic multiblock molecules and copolymers are highlighted, where linear molecules not only undergo folding elaborately but also form controlled and compartmentalized self-assemblies to realize characteristic functions in solution, the crystalline state, and membranous media.