Abstract: Sample preparation of naturally occurring matrices necessitates the development of highly sensitive and selective methods for the extraction and preconcentration of biologically active compounds. Smart materials are highly promising in this area and are selected for solving for specific analytical tasks. This review examines the main categories of such materials, including ionic liquids, eutectic solvents, nanomaterials, metal-organic frameworks, covalent organic frameworks, and molecularly imprinted polymers. It highlights their unique properties and provides specific examples of their application to chemical analysis between 2020 and 2025. The article discusses the use of smart materials in the analysis of biological fluids and environmental samples, available microextraction techniques, and subsequent quantification methods. It emphasizes the advancements achieved in comparison to the previously established approaches.