A novel protein/polysaccharide complexation was found when unfolded ferricytochrome c (Cyt-c) was mixed with denatured schizophyllan (SPG) and the renaturation of both protein and polysaccharide was carried out simultaneously. Upon the complexation, the Q band was split, indicating that ferric Cyt-c was converted into the ferrous state. The changes in circular dichroism and fluorescence from tryptophan showed that the entire protein conformation was drastically deformed.