Asymmetric bipolar membranes modified with phosphorylated and carboxylated hyperbranched polymers with different degrees of functionalization have been synthesized and studied. The effect of the nature of ionogenic groups of functionalized polymers on both individual electrochemical characteristics of asymmetric bipolar membranes and their efficiency in adjusting the pH of dilute solutions by electrodialysis has been studied. It has been found that an increase in the degree of functionalization of hyperbranched polymers leads to an increase in the current efficiency and a decrease in the voltage drop across the asymmetric bipolar membranes.