Enantiomeric biomaterials which are mirror images of each other are characterized by chiral degeneracy--identical structural characteristics and bulk material properties. The addition of another chiral component, D-polysaccharide, has been shown to split such degeneracy and result in two distinct biomaterials. Dynamic oscillatory rheometry and small-angle X-ray scattering demonstrate that the natural biochirality combination of L-peptides and D-polysaccharides assembles faster, has higher elastic moduli (G'), and is structurally more beneficial as opposed to the alternative D-peptide and D-polysaccharide combination. Chemical modifications of the OH-groups in α-D-glucose units in D-polysaccharides weaken such splitting of chiral degeneracy. These findings form a basis to design novel biomaterials and provide additional insight on why proteins and polysaccharides have oppoiste chirality in the biological world.