The particular molecular-electronic structure and properties of different genera of vegetable fibers (such as cotton, jute, sisal, pineapple) have been studied with ESR in combination with many other methods. A complicated Fivefold Metallo-Organic Aperiodic Crystal Structure of the Vegetable Fiber has been discovered. This structure plays a decisive role in the formation of an "elementary fiber" as well as of a "macroscopic practical fiber" and in the specific features of the fibers.