Enzyme-assisted extraction is a valuable tool for mild and environmentally-friendly extraction conditions to release bioactive compounds and sugars, essential for silver nanoparticle (AgNP) green synthesis as capping and reducing agents. In this research, plant and fungal kingdoms were selected to obtain the enzyme-assisted extracts, using green synthesized AgNPs. For the synthesis, pseudo-cereal Fagopyrum esculentum (F. esculentum) and lichen Certaria islandica (C. islandica) extracts were used as environmentally-friendly agents under heating in an aqueous solution. Raw and enzyme-assisted extracts of AgNPs were characterized by physicochemical, phytochemical, and morphological characteristics through scanning and transmission electron microscopy (SEM and TEM), as well as Fourier transform infrared spectroscopy (FTIR). The synthesized nanoparticles were spherical in shape and well dispersed, with average sizes ranging from 10 to 50 nm. This study determined the total phenolic content (TPC) and in vitro antioxidant activity in both materials by applying standard methods. The results showed that TPC, ABTS•+, FRAP, and DPPH• radical scavenging activities varied greatly in samples. The AgNPs derived from enzymatic hydrolyzed aqueous extracts C. islandica and F. esculentum exhibited higher antibacterial activity against the tested bacterial pathogens than their respective crude extracts. Results indicate that the extracts’ biomolecules covering the AgNPs may enhance the biological activity of silver nanoparticles and enzyme assistance as a sustainable additive to technological processes to achieve higher yields and necessary media components.