High proton conductive xCsHSO(4)-(1-x)H4SiW12O40(CHS-WSiA) composites were successfully prepared via a new liquid-phase shaking method. N,N-Dimethylacetamide (DMAc) and zirconium balls were used as a solvent/dispersing medium and a collision medium, respectively. X-ray diffraction characterization confirmed that the liquid-phase shaking treatment induced an ion-exchange reaction between Cs+ ions in CHS and H+ ions in WSiA to form new composite materials. The proton conductivities of these composites were significantly improved over their precursor materials, especially at low temperatures, below the superprotic phase-transition temperature of CHS. The 0.9CHS-0.1WSiA (in mole ratio) composite, for instance, showed the highest proton conductivities of 1.38 x 10(-4) to 2.42 x 10(-3) S cm(-1) from 50 degrees C to 170 degrees C under dry conditions of nitrogen atmosphere. The enhanced anhydrous proton conductivities of the Cs-substituted WSiA composites were also corroborated with shortening of the hydrogen bonding distance in these composites for fast proton hopping transport mechanism via H-1 NMR evaluation.