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Green Analytical Chemistry has led to the research and development of more sustainable analytical methodologies, focusing on the miniaturization of extraction methods, the incorporation of new smart materials, and automation. In this sense, metal–organic frameworks (MOFs) and covalent–organic frameworks (COFs) have attracted considerable attention as novel sorbent materials to be incorporated in Analytical Chemistry over the last decade. These highly ordered crystalline structures, constituted by the assembly of different molecular building blocks through coordination or covalent bonds, respectively, present outstanding characteristics, such as high surface areas and porosity, good thermal and mechanical stabilities, and impressive tunability. This book chapter gives an overview of the preparation of MOFs and COFs for their implementation in green analytical microextraction, particularly highlighting their uses in various working modes of micro-solid-phase extraction, solid-phase microextraction, thin-film microextraction, and stir-bar sorptive extraction.