Hierarchical porous structures with different levels of porosity allow for efficient diffusion of guests through the network of pores and channels, making them promising materials for a wide range of applications including gas adsorption, separation, and catalysis. Although many approaches have been attempted to increase the pore size of metal–organic framework (MOF) materials, it is still a challenge to construct MOFs with customized hierarchical porous architectures. In this talk, we present a new method, linker labilization, to increase the porosity and pore size of microporous MOFs, giving rise to hierarchical-pore MOFs. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.