Polyflavonoid tannin autocondensation was found to be facilitated by the reaction occurring on cellulose and lignocellulosic substrates. Although the mechanism of polyflavonoid autocondensation induced by cellulose differs from that induced by the action of Lewis acids, the subsequent reaction of autocondensation appears to be similar. The determining step of tannin rearrangement pathways under alkaline conditions in cellulose-induced higher-temperature autocondensation is the favoring of the heterocycle pyran ring opening over the normal interflavonoid bond cleavage and catechinic acid rearrangement. This is caused by relevant bond weakening and easier cleavage induced by strong attractive forces between flavonoid and cellulosic substrate. Applied bonding of cellulosic substrates by polyflavonoid tannin autocondensation reactions appears to be feasible and to occur as predicted from theoretical predictions.