Metal–organic frameworks (MOFs) are porous hybrid materials composed of metal ions and organic linkers, characterized by many unique properties, of which the most important are their crystallinity, the highest known surface areas, mechanical and thermal stability, selectivity, and reusability. As the adoption of MOFs can easily meet the principles of Green Analytical Chemistry (GAC), analytical chemistry has benefited a lot from the potential of MOF applications. MOFs have proven to be successful as sorbent materials in extraction/microextraction processes, as sensors, and as stationary or pseudo-stationary phases in chromatographic systems. However, considering the GAC principles, assurance of MOF sustainability must begin with MOF design, followed by an adequate synthetic methodology and toxicity evaluation of the resulting material, resulting in an analytical methodology that can be categorized as a GAC procedure. Taking all of these into consideration, a significant collaboration between materials science and analytical chemistry, with an emphasis on green chemistry, should be encouraged and strengthened. This chapter places particular emphasis on the efforts in making MOF synthesis greener and on the various routes and methods explored. In addition, the use of green approaches in the preparation of MOFs and/or in their incorporation into less-harmful analytical chemistry methods is discussed.