Critical materials (CMs) are a group of elements that have been determined to be important for the modern economy, but which may face current or potential supply limitations. Some examples of metals that have received the CM designation include the rare earth elements, indium, gallium, and lithium. The last decade has seen a major push for the development of new and improved technologies for the recovery and purification of CMs from various traditional and non-traditional resources in an effort to diversify supply. Solid-phase extraction (SPE) is one broad category of these experimental extraction technologies. SPE involves the application of a solid material to preferentially retain in the solid phase one or more specific components of an aqueous solution, leaving the other components behind in the aqueous phase. A wide range of different sorbents has been used for SPE, and many offer significant potential advantages, including low cost, low environmental impact, and high customizability. Hierarchically porous silica monoliths are one example of a cutting-edge sorbent that provides a durable, high surface area foundation that can be functionalized with a variety of targeted ligands for the selective extraction of specific CMs. Despite impressive recent advances in SPE, there remain areas for improvement that are common across the discipline. To demonstrate the practical viability of these innovative CM recovery systems, future SPE studies would benefit from devoting additional focus to the scalability of their material, as well as from focusing on real-world feedstocks and conducting techno-economic analyses and environmental impact studies.