It is a significant challenge to develop proton exchange membranes (PEMs) possessing both desired proton conductivity and low methanol permeability for the direct methanol fuel cells (DMFC). In this work, a composite PEM was fabricated from a predominantly hydrophobic framework of three-component polymer blend (TCPB) of acrylic polymers and a dispersed proton-conducting hydrophilic copolymer network. The hydrophilic copolymer was designed to contain three co-monomer units of complementary functionalities: 2-acrylamido-2-methyl propanesulfonic acid (AMPS), 2-hydroxyethyl methacrylate (HEMA), and 2-hydroxyl-3-(diethanolamino)propylmethacrylate (DEAPMA). The resultant PEMs were macroscopically homogeneous but contained microscopic heterogeneity in the form of dispersed nanosize AMPS domains with radiating (HEMA-DEAPMA) segments in the TCPB matrix, forming an overall amphiphilic matrix. Formation of such a texture was consequential upon the association of AMPS units and hydrogen bonding between the HEMA and DEAPMA short blocks of the hydrophilic copolymer with TCPB. The polymer blend membranes therefore acquired dual functionalities, i.e., effective proton transport between AMPS granules through interconnecting (HEMA-DEAPMA) segments, resulting in proton conductivity of the order of 10(-2) S/cm, and low water uptake and inhibited methanol passage in the continuous amphiphilic matrix, resulting in methanol permeability of (1.25-8) x 10(-7) cm(2)/s, which is about 3-8 times smaller than that of Nafion117.