Poly(diallyldimethylammonium chloride) (p-DADMAC) increases the rate of alpha-amylase-induced cornstarch liquefaction, thereby reducing the enzyme dose necessary for optimal hydrolysis. A similar increase is also provided by cationic polyacrylamides (c-PAMs), but p-DADMAC offers the added industrial benefits of lower cost, a lower catalytic concentration, and a much lower residual in distillers dry grain. p-DADMAC also increases enzyme-substrate binding, lowers the onset temperature of gelatinization, and reduces the viscosity of the gelatinized cornstarch. It is proposed that most of these benefits result from the higher charge density of p-DADMAC, which neutralizes the negative charge on the cornstarch at a lower polymer dose. The higher charge also inhibits the agglomeration of starch through charge reversal. These attributes of p-DADMAC offer cost and performance benefits that can be realized in existing corn ethanol facilities.