Metal-Organic Frameworks (MOFs) are an emerging class of porous materials constructed from metal-containing nodes and organic linkers. Due to their structural and functional tunability as well as ever-expanding application scope, MOFs have become one of the most fascinating class of materials. Many early carboxylate MOFs made from divalent metals showed exceptional porosity and promise for a wide variety of applications, but ultimately proved unsuitable for use under harsh conditions because of their lack of stability. To improve the robustness, we have been focusing on the development of stable carboxylate MOFs based on tri- and tetravalent metals (M (III) and M (IV)), which tend to possess much greater stability due to the increased strength and kinetic inertness of the M−O bonds. The exceptional stability of M (III) and M (IV) based carboxylate MOFs have made them feasible for use in a wide-range of practical applications. However, on the other hand, the inertness of the metal‒carboxylate bonds has posed a synthetic challenge for the preparation of the M (III) and M (IV) MOFs. Multiple synthetic strategies based on judicious kinetic control have been developed, which have led to a MOF toolkit, through which a target MOF can be retro-synthetically designed and synthesized. Prior to the present work, MOFs were formed via “one-pot” approaches almost exclusively. To form carboxylate MOFs from M (III) and M (IV), the following synthetic strategies have been developed: First, we explored a method of kinetically-tuned dimensional augmentation of robust clusters with terminal carboxylate groups by tuning the kinetics of the synthetic procedure. Secondly, we developed post-synthetic metathesis and oxidation reactions, where redox chemistry is applied to mediate bridging ligand exchange. Thirdly, we invented a sequential linker installation method, through which up to three different linkers can be installed into a MOF with a crystallographically ordered structure. Most recently, we enriched the MOF synthetic tool box by introducing linker labilization, in which selective linkers were exchanged, cleaved, and removed to create MOFs with hierarchical pore structures controllably. Together the MOF toolkit enables the preparation of a target MOF retrosynthetically, just like that of a natural product. These MOFs are critical for a variety of applications including gas storage and separation, chemical sensing, energy harvesting and storage, catalysis, as well as biomedicine.