There is a wide range of renewable materials with attractive prospects for the development of green technologies for the removal and recovery of metals from aqueous streams. A special category among them are natural fibers of biological origin, which combine remarkable biosorption properties with the adaptability of useful forms for cleanup and recycling purposes. To support the efficient exploitation of these advantages, this article reviews the current state of research on the potential and real applications of natural cellulosic and protein fibers as biosorbents for the sequestration of metals from aqueous solutions. The discussion on the scientific literature reports is made in sections that consider the classification and characterization of natural fibers and the analysis of performances of lignocellulosic biofibers and wool, silk, and human hair waste fibers to the metal uptake from diluted aqueous solutions. Finally, future research directions are recommended. Compared to other reviews, this work debates, systematizes, and correlates the available data on the metal biosorption on plant and protein biofibers, under non-competitive and competitive conditions, from synthetic, simulated, and real solutions, providing a deep insight into the biosorbents based on both types of eco-friendly fibers.