Transition metal-based layered double hydroxidesLayered double hydroxides (TM-LDHs) have gained significant attention in analytical chemistry due to their unique properties such as easy synthesis, low cost, high specific surface area, strong catalytic activity, and biocompatibility. Their use in sample extraction, electrochemical sensing, and colorimetric detection highlights their versatility for various applications. Solid-phase microextraction (SPME) using LDHs offers advantages like high surface area, low operating pressure, and ease of production and purification. Microextraction techniques minimize the use of sorbent materials and organic solvents, making them more environmentally friendly and cost-effective compared to traditional SPE methods. However, their lower sorbent loadings result in relatively lower sensitivity. This chapter explores the application of transition metal-based LDHs as effective sorbents in overcoming this limitation in various solid-phase extraction (SPE) and microextraction techniques, including dispersive microSolid phase extraction solid-phase extractionDispersive micro solid phase extraction (D-µ-SPE), in-tubeIn-tube SPME SPMEIn-Tube Solid-Phase Microextraction (IT-SPME) (IT-SPME), headspace SPMEHead Space Solid Phase Microextraction (HS-SPME) (HS-SPME), stir bar sorptive extractionStir bar sorptive extraction (SBSE), and thin film microextractionThin film microextraction (TFME). The key aspects discussed include the principles of these techniques, parameters affecting extraction efficiency, analytical figures of merit achieved, and how the benefits of LDH sorbents (high surface area and anion exchange capacity) can enhance extraction sensitivity and enable extraction of a wide range of analytes from complex sample matrices.