The decisive role of metallic cations in the formation of supramolecular clusters involving lignin, cellulose, and hemi-cellulose and its relationship to energy losses in ruminants associated with fibrous feed resources is still not well understood. Indeed, interactions between lignin, cellulose and metallic cations generate highly stable clusters that significantly decrease the capability of cellulase to break bonds between sugar units in order to facilitate the absorption of a great quantity of cellulose, which is ingested by ruminants as forage. Furthermore, several metallic cations cannot be absorbed as a consequence of the formation of coordinated ligations with the oxygen atoms of the lignocellulosic cluster. The loss of lignocellulose-metal clusters by ruminants is responsible for a substantial waste of nutrients, which is a significant problem in animal science. Moreover, the chemical structure of these relevant supramolecular systems is poorly understood. In the present review, we discussed this topic in detail in reference to relevant literature from the chemical and animal sciences in order to analyze the perspectives associated with the improvement of nutritional absorption from feed resources by ruminants.