The demand for the recovery of valuable metals and the need to understand the impact of heavy metals in the environment on human and aquatic life has led to the development of new methods for the extraction, recovery, and analysis of metal ions. With special emphasis on environmentally friendly approaches, efforts have been made to consider strategies that minimize the use of organic solvents, apply micromethodology, limit waste, reduce costs, are safe, and utilize benign or reusable materials. This review discusses recent developments in liquid- and solid-phase extraction techniques. Liquid-based methods include advances in the application of aqueous two- and three-phase systems, liquid membranes, and cloud point extraction. Recent progress in exploiting new sorbent materials for solid-phase extraction (SPE), solid-phase microextraction (SPME), and bulk extractions will also be discussed.