Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix "Tordis" (Salix schwerinii x Salix viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by thesemetallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.