Surface structures of rod–coil block copolymer brushes with different architectures tethered to a surface showed distinct surface structures under different grafting densities and lengths of the coil blocks [129] (Fig. 35). Compared with the linear structure, the Y-shaped rod–coil brushes proceeded much faster with respect to the surface grafting density because each Y-shaped brush contains two rod blocks. The aggregated sizes formed by the rod blocks increased with enhancing the grafting density for both the linear and Y-shaped rod–coil brushes. However, for Y-shaped polymer brushes, isolated islands of aggregates can only survive at a low surface grafting density, transforming into wormlike, interconnected, honeycomb, and fully covered structures as the grafting density increases. On the other hand, comb-like brushes exhibited surface structures distinct from those of linear and Y-shaped brushes. Aggregates with the shapes of cone, cylinder, and layers of spheres were observed depending on the size of the gap between each rod blocks. These results provide a guide for designing the polymer brushes with desired surface structures and thus desired properties.