Abstract: Sample pretreatment is a crucial step in trace analysis, and its efficiency greatly depends on the enrichment effect and matrix cleanup performance of extraction materials. Therefore, the development of efficient extraction materials remains a core research focus in this field. Graphene (G) and graphene oxide (GO) were recognized as exceptional extraction materials due to their high specific surface area, large π-conjugated structure, and strong adsorption capability. However, several drawbacks were noted, including easy agglomeration, poor extraction selectivity, and slow mass transfer. To overcome these limitations, chemical modification and functionalization strategies were extensively employed, leading to functionalized graphene-based sorbents for solid-phase extraction (SPE) and solid-phase microextraction (SPME). Based on research works between 2022 and 2025, this review systematically summarized the advances of G, GO, and their functionalized composites in SPE and SPME. Efficient extraction of diverse analytes, such as polycyclic aromatic hydrocarbons, pesticide residues, food additives, stimulants, amino acids, and heavy metal ions, was achieved. Multiple interaction mechanisms, including π-π stacking, hydrophobic effects, electrostatic attraction, and hydrogen bonding, played essential roles in determining extraction efficiency and selectivity. The SPE and SPME methods coupled with chromatographic detection were successfully applied in environmental monitoring (water and soil pollutants), food safety (screening of pesticides and illegal additives), biochemical analysis (urine and herbal medicines), and forensic toxicology (drug analysis), consistently offering high extraction efficiency, good analytical sensitivity, and operational convenience. To address the inherent drawbacks of G, the research focus was shifted from simple material utilization toward an integrated strategy comprising structural design, composite fabrication, and extraction mode innovation. Structurally, three-dimensional aerogels, interlayer spacers, and porous substrates were constructed to effectively inhibit the restacking of G nanosheets, thereby markedly improving adsorption capacity and mass-transfer efficiency. Functionally, different composites were fabricated or surface modifications with covalent organic frameworks, metal-organic frameworks, and ionic liquids, imparting multiple interaction sites to the sorbents and enabling a transition from non-specific adsorption to selective enrichment. In extraction mode, emerging auxiliary approaches, including electrically enhanced and cold-assisted extraction, were combined to substantially optimize extraction kinetics and enrichment factors. Consequently, graphene-based extraction materials served as a bridge linking complex raw samples with accurate instrumental quantification. Six future trends were identified. First, the upgrading of composite modification was emphasized: advanced hybrid materials can be constructed through in-situ growth, sol-gel synthesis, or self-assembly strategies, and the introduction of affinity groups, chelating sites, or molecularly imprinted cavities will greatly enhance selectivity and stability. Second, the hyphenation of graphene-based extraction materials with advanced detection techniques is highlighted: Online SPE is envisioned for automatic sampling, adsorption, and elution, while online SPME is designed for automated extraction and injection via autosampler accessories, thereby promoting the seamless coupling of pretreatment protocols with sensitive platforms such as GC-MS/MS, HPLC-MS, ICP-MS, and digital colorimetric analysis for integrated full-process analysis. Third, the expansion into complex matrices from diverse fields is a major direction, with the aim of resolving the technical bottlenecks of highly interfering sample pretreatment, mitigating matrix effects, and improving the reliability of trace-level detection. Fourth, green synthesis of graphene-based materials and solvent-free extraction procedures are prioritized: low-toxic or non-toxic synthetic methods should be developed, and the consumption of organic solvents during extraction is intended to be reduced. Fifth, the development of portable and intelligent extraction devices is regarded as an urgent requirement, driven by the growing demand for on-site detection and the progress of detection technologies. Sixth, the application of external field-assisted techniques is proposed as a promising approach: novel extraction modes such as electrically intensified and magnetically driven extraction are expected to be developed, which will further accelerate mass transfer and simplify material recycling. Collectively, these six trends fully conform to the modern developmental requirements of analytical chemistry—high efficiency, precision, environmental friendliness, and automation.

Key words: graphene (G), graphene oxide (GO), solid-phase extraction (SPE), solid-phase microextraction (SPME), chromatographic analysis