Herbal medicine (HM) is crucial in disease management and contains complex compounds with few active pharmacological ingredients, presenting challenges in quality control of raw materials and formulations. Effective separation, identification, and analysis of active components are vital for HM efficacy. Traditional methods like liquid‐liquid extraction and solid‐phase extraction are time‐consuming and environmentally concerning, with limitations such as sorbent issues, pressure, and clogging. Magnetic solid‐phase extraction uses magnetic sorbents for targeted analyte separation and enrichment, offering rapid, pressure‐free separation. However, inorganic magnetic particles’ aggregation and oxidation, as well as lack of selectivity, have led to the use of various coatings and modifications to enhance specificity and selectivity for complex herbal samples. This review delves into magnetic composites in HM pretreatment, specifically focusing on encapsulated or modified magnetic nanoparticles and materials like silica, ionic liquids, graphene family derivatives, carbon nanotubes, metal‐organic frameworks, covalent organic frameworks, and molecularly imprinted polymers.