In recent years, porous polymers have gained significant attention for their application as powerful and selective sorbents in micro solid phase extraction (µSPE). In this review we explore the preparation and utilization of various porous polymer sorbents, highlighting their impact on enhancing µSPE techniques. Molecularly imprinted polymers (MIPs), graphene oxide-modified frameworks, and zeolitic imidazole frameworks (ZIFs) are among the innovative materials discussed. These innovative materials have significantly improved µSPE methods, offering enhanced extraction efficiencies, superior selectivity, and reduced solvent consumption, all of which align with the principles of green chemistry. Key findings of this review include the demonstration that MIPs exhibit excellent target specificity, making them ideal for complex matrices, while graphene oxide frameworks and ZIFs provide increased surface area and stability for diverse analytical applications. Despite these advancements, challenges remain, particularly the high cost of certain innovative materials, limited reusability, and the absence of automation in µSPE workflows. Furthermore, controlling the precise synthesis and functionalization of these sorbents continues to be a limiting factor. To address these issues, future research should focus on developing cost-effectiveness methods, the use of biopolymer or sustainable feedstocks, and scalable synthesis methods; integrating automation into µSPE; and exploring new polymeric materials with enhanced properties. Additionally, novel hybrid materials that combine the strengths of multiple sorbents offer a promising direction for future exploration. We critically analyze the advantages and limitations of each sorbent type, providing a comprehensive overview of their applications in µSPE. This paper also examines the synthesis, characterization, and unique properties of these porous polymers, emphasizing their role in advancing analytical chemistry towards more efficient and environmentally friendly practices. The need for continued development of high-performance, low-cost, and sustainable sorbents is underscored to further enhance the effectiveness of µSPE techniques.