A comprehensive study of the adsorption abilities of Saccharomyces cerevisiae cell wall components towards aflatoxin B1, deoxynivalenol, zearalenone, patulin and ochratoxin A was achieved in vitro. The comparison of several sources of yeast cell wall differing in their relative glucan/mannan/chitin showed a strong involvement in the adsorption process of the beta-D-glucan moiety, composed of linear chains of (1,3)-beta-D-glucans branched with (1,6)-beta-D-glucan side chains. Affinity rates varied widely between toxins due to their structural and physico-chemical disparities. The chemical interaction approached by molecular mechanics, NMR, X-ray structural data analysis, demonstrated the importance of the single and/or triple helix organization of beta-D-glucans. We emphasized that chemical interactions involved weak but multiple chemical hydrogen and van der Waals bonds leading to the chemical encagment of mycotoxins into the helix-shaped (1,3)-beta-D-glucan structure firmly stabilized by the (1,6)-beta-D-glucan side branching providing a high geometric complementarity's and stability to the overall system.