Polymeric phosphonic acid submicrospheres (PPASs) with carboxylic acid cores and phosphonic acid shells are synthesized by distillation-precipitation polymerization. The structure and composition of PPASs are confirmed by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and energy dispersive X-ray (EDX). The PPASs are then incorporated into sulfonated poly(ether ether ketone) (SPEEK) to fabricate composite membranes for direct methanol fuel cells (DMFCs). The incorporated PPASs enlarge the ion-channel size of the composite membranes as testified by small-angle X-ray scattering (SAXS), affording significantly enhanced water uptake and water retention. Compared with the membrane containing the polymeric carboxylic acid submicrospheres (PCASs), the PPASs-filled membrane exhibits higher proton conductivity owing to the higher water uptake and water retention of the PPASs and stronger acidity of phosphonic acid. The composite membrane with 15 wt.% PPASs displays the highest proton conductivity of 0.0187 S cm(-1) at room temperature and 100% relative humidity (RH). At the RH as low as 20%, this membrane acquires a proton conductivity of 0.0066 S cm(-1), 5 times higher than that of the SPEEK control membrane (0.0011 S cm(-1)) after 90 min testing, at 40 degrees C. (C) 2012 Elsevier B.V. All rights reserved.