Dynamic covalent chemistry (DCvC) provides an intriguing and highly efficient approach for building molecules that are usually thermodynamically favored. However, the DCvC methods that are efficient enough to construct large, complex molecules, particularly those with three-dimensional (3-D) architectures, are still very limited. Alkyne metathesis as a quickly emerging DCvC method is rarely applied to 3-D organic cage assemblies. The objective of the work described in this book is to discuss the efficient assembly of 3-D shape-persistent covalent organic polyhedrons(COPs) through dynamic alkyne metathesis and study the relationship of the COP structures and the geometry of their building blocks. These arylene-ethynylene COPs show great potential in fullerene separations.