Desymmetrization self-assembly of symmetric building blocks is a powerful method to construct elaborate metallosupramolecular architectures. Herein several examples are given to discuss how to build up self-assembled complexes with low symmetry, focusing on 1) stabilization of local structural motifs by template molecules and/or interligand interactions, 2) rigidity regulation of ligand scaffolds, and 3) control of intermediate complexation conditions. Unsymmetrically assembled supramolecular host complexes exhibit unique functions reflecting their structural frameworks.