Hierarchically ordered microstructures, self-assembled from copolymers, have drawn considerable attentions in the last decades. Study of hierarchical microstructure impacts many realms such as material engineering and biology science. In this article, notable recent advances in the fields of hierarchical polymeric microstructures generated in either bulk or selective solvents are highlighted, from both the experimental and theoretical/simulation aspects. The polymer systems for the hierarchical microstructures are concentrated on multiblock copolymers and polymer blends with/without non-covalent bonding interactions. Particular emphasis is placed on what governs the self-assembly of hierarchical microstructures from a diversity of designed copolymer systems, how to classify the types of non-frustrated and frustrated hierarchical structures, and where the future opportunities are. (C) 2013 Elsevier Ltd. All rights reserved.