The mass production of hierarchically porous metal-organic frameworks (HP-MOFs) with adjustable morphology and size as well as retained crystallinity is highly desirable yet challenging. Herein, we have developed a versatile post-synthetic ligand substitution (PSLS) strategy to convert typical microporous MOFs and even their composites to HP-MOFs and their composites at a 10 g level and beyond in a simple reflux system. The resulting HP-MOFs feature intrinsic micropores and abundant defective mesopores, which greatly facilitate the transport and activation of large substrates for stable and efficient heterogeneous catalysis. Furthermore, the presence of defective mesopores in the HP-MOF composites improves activity and selectivity for large molecule-involved one-pot tandem catalysis. This strategy opens a new door to fast, facile, general, and scale-up production of HP-MOFs and related composites for expanding applications of conventional microporous MOF-based materials.