There are many ways to obtain metal nanoparticles: biological, physical, and chemical ways and combinations of these approaches. Synthesis assisted with plant extracts has been widely documented. However, one issue that is under discussion refers to the metabolites responsible for reduction and stabilization that confine nanoparticle growth and prevent coalescence between nanoparticles in order to avoid agglomeration/precipitation. In this study, Ag nanoparticles were synthesized using organic extracts ofChenopodium ambrosioideswith different polarities (hexane, dichloromethane, and methanol). Each extract was phytochemically characterized to identify the nature of the metabolites responsible for nanoparticle formation. With methanol extract, the compounds responsible for reducing and stabilizing silver nanoparticle were associated with the presence of phenolic compounds (flavonoids and tannins), while, with dichloromethane and hexane extracts, the responsible compounds were mainly terpenoids. Large part of the reducing activity of secondary metabolites inC. ambrosioidesis closely related to compounds with antioxidant capacity, such as phenolic compounds (flavone glycoside and isorhamnetin), which are the main constituents of the methanol extracts. Otherwise, terpenoids (trans-diol,α-terpineol, monoterpene hydroperoxides, and apiole) are the central metabolites present in dichloromethane and hexane extracts.