Copolymers of acrylic acid and styrene with styrene unit contents of 2.7, 5.7, and 9.5% were synthesized by free radical copolymerization. Poly(ethylenimine)s with benzylated unit contents of 2.4, 6.0, 10.6, and 16.7% were obtained by the reaction of poly(ethylenimine) with benzyl bromide. Polyelectrolyte complex capsules consisting of these polymers were prepared. Influence of the hydrophobic units on pH-responsive release property of the capsules was studied using phenylethylene glycol as a permeant. When the copolymer with styrene unit content of 5.7% or the poly(ethylenimine) with the benzylated unit content of 2.4-10.6% was used as the membrane components, the permeability of the capsule membrane became minimum and was 10-20 fold lower than that of the poly(acrylic acid)-poly(ethylenimine) complex capsule membrane in the pH region between 3 and 7. In contrast, the hydrophobic units did not lower the permeability of the capsule membranes significantly below pH 3 and above pH 7. Thus, the capsule membranes containing hydrophobic units exhibited remarkable permeability changes in the narrow pH regions of 2-3 and 7-9. Also, the capsule containing the benzylated PEI in the membrane changed the release rate of the contents very quickly, in response to the ambient pH alteration. Therefore, polyelectrolyte complex capsules, which are highly sensitive to pH change, were obtained by using the polyelectrolytes with the hydrophobic units as membrane components.