This review explores the advances in developing adsorbent materials for solid-phase microextraction (SPME), focusing on nanoparticles, nanocomposites, and nanoporous structures. Nanoparticles, including those of metals (e.g., gold, silver), metal oxides (e.g., TiO2, ZnO), and carbon-based materials (e.g., carbon nanotubes, graphene), offer enhanced surface area, improved extraction efficiency, and increased selectivity compared to traditional coatings. Nanocomposites, such as those combining metal oxides with polymers or carbon-based materials, exhibit synergistic properties, further improving extraction performance. Nanoporous materials, including metal–organic frameworks (MOFs) and ordered mesoporous carbons, provide high surface area and tunable pore structures, enabling selective adsorption of analytes. These advanced materials have been successfully applied to various analytes, including volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), pesticides, and heavy metals, demonstrating improved sensitivity, selectivity, and reproducibility compared to conventional SPME fibers. The incorporation of nanomaterials has significantly expanded the scope and applicability of SPME, enabling the analysis of trace-level analytes in complex matrices. This review highlights the significant potential of nanomaterials in revolutionizing SPME technology, offering new possibilities for sensitive and selective analysis in environmental monitoring, food safety, and other critical applications.
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