Zirconium‐based metal‐organic framework materials (Zr−MOFs) have more practical usage over most conventional benchmark porous materials and even many other MOFs due to the excellent structural stability, rich coordination forms, and various active sites. However, their mass‐production and application are restricted by the high‐cost raw materials, complex synthesis procedures, harsh reaction conditions, and unexpected environmental impact. Based on the principles of “Green Chemistry”, considerable efforts have been done for breaking through the limitations, and significant progress has been made in the sustainable synthesis of Zr−MOFs over the past decade. In this review, the advancements of green raw materials and green synthesis methods in the synthesis of Zr−MOFs are reviewed, along with the corresponding drawbacks. The challenges and prospects are discussed and outlooked, expecting to provide guidance for the acceleration of the industrialization and commercialization of Zr−MOFs.

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Metal‐organic framework (MOF) gel, an emerging subtype of MOF structure, is unique in formation and function; however, its evolutionary process remains elusive. Here, the evolution of a model gel‐based MOF, UiO‐66(Zr) gel, is explored by demonstrating its sequential sol‐gel self‐assembly and nonclassical gel‐crystal transformation. The control of the sol‐gel process enables the observation and characterization of structures in each assembly stage (phase‐separation, polycondensation, and hindered‐crystallization) and facilitates the preparation of hierarchical materials with giant mesopores. The gelation mechanism is tentatively attributed to the formation of zirconium oligomers. By further utilizing the pre‐synthesized gel, the nonclassical gel‐crystal transformation is achieved by the modulation in an unconventional manner, which sheds light on crystal intermediates and distinct crystallization motions (“growth and splitting” and “aggregation and fusion”). The overall sol‐gel and gel‐crystal evolutions of UiO‐66(Zr) enrich self‐assembly and crystallization domains, inspire the design of functional structures, and demand more in‐depth research on the intermediates in the future.