Nanozymes (NZs) are catalytically active nanomaterials that have enzyme-like activity but possess increased stability and greater availability due to the fact of their simpler preparation technologies. Nanozymes as nanoscale artificial enzymes demonstrate various catalytic specificities as oxidoreductases, such as peroxidase, catalase, laccase, and others as well as hydrolases, proteases, endonucleases, DNA-ases, NO synthases, etc. A broad variety of NZs exhibits dual- or multienzyme mimetic activity. Nanozymes as stable, low-cost mimetics of natural enzymes have a high potential for application in different branches of biotechnology including scientific investigations, industry, and ecology. Nanozymes can be applied in medicine as diagnostic tools and components of therapeutic drugs. Since NZs have high catalytic activity and chemical and biological stability, they are very promising in the construction of biosensors and biofuel cells. For these reasons, the search for simple methods of synthesis and characterization of different NZs is a very important and real problem. The “green” synthesis of Prussian blue analogous as peroxidase-like NZs using oxido-reductases is described in this study. The obtained green-synthesized hexacyanoferrates (gHCFs) of transition metals were characterized by structure, size, composition, catalytic properties, electro-mediator activities, and substrate specificity. Copper hexacyanoferrate (gCuHCF) was studied in more detail. When immobilized on a graphite electrode (GE), gCuHCF under special conditions of pH and tension gave amperometric signals on hydrogen peroxide and can be used as a peroxidase mimetic in oxidase-based biosensors. Under other conditions, gCuHCF/GE reacts to other analytes. We propose that gHCFs of transition metals synthesized via enzymes may become prospect platforms for the construction of multi-functional amperometric (bio)sensors.