The animal hormone melatonin (N-acetyl-5-methoxytryptamine) is a pleiotropic molecule with multiple and various functions. Phytomelatonin is the melatonin from plants and was discovered in 1995 in some species. Phytomelatonin is considered an interesting molecule in the physiology of plants, as it seems to be involved in many actions, such as germination, growth, rooting and parthenocarpy, including fruit set and ripening; it also seems to play a role during postharvest. It has been studied in processes such as primary and secondary metabolism, photosynthesis and senescence, as well as in the nitrogen and sulfur cycles. Phytomelatonin up- and down-regulates many relevant genes related to plant hormones and key genes related to the above-mentioned aspects. One of the most decisive aspects of phytomelatonin is its relevant role as a bioprotective and alleviating agent against both biotic and abiotic stressors, which has opened up the possibility of using melatonin as a phytoprotector and biostimulant in agriculture. In this respect, using material of plant origin to obtain extracts rich in phytomelatonin instead of using synthetic melatonin (thus avoiding unwanted by-products) has become a topic of discussion. This work characterized the phytomelatonin-rich extracts obtained from selected herbs and determined their contents of phytomelatonin, phenols and flavonoids; the antioxidant activity was also measured. Finally, two melatonin-specific bioassays in plants were applied to demonstrate the excellent biological properties of the natural phytomelatonin-rich extracts obtained. The herb composition and the protocols for obtaining the extracts rich in phytomelatonin are in the process of registration for their legal protection.