By changing -COOH content in poly(acrylic acid-co-methacryloxypropyl trimethoxy silane (poly(AA-co-gamma-MPS)), a series of PVA/SiO2 cation exchange membranes are prepared from sol-gel process of poly(AA-co-gamma-MPS) in presence of poly(vinyl alcohol) (PVA). The membranes have the initial decomposition temperature (IDT) values of 236-274 degrees C. The tensile strength (TS) ranges from 17.4 MPa to 44.4 MPa. The dimensional stability in length (DS-length) is in the range of 10%-25%, and the DS-area is in the range of 21%-56% in 65 degrees C water. The water content (W-R) ranges from 61.2% to 81.7%, the ion exchange capacity (IEC) ranges from 1.69 mmol/g to 1.90 mmol/g. Effects of -COOH content on diffusion dialysis (DD) performance also are investigated for their potential applications. The membranes are tested for recovering NaOH from the mixture of NaOH/Na2WO4 at 25 - 45 degrees C. The dialysis coefficients of NaOH (U-OH) are in the range of 0.006-0.032 m/h, which are higher than those of the previous membranes (U-OH: 0.0015 m/h, at 25 degrees C). The selectivity (S) can reach up to 36.2. The DD performances have been correlated with the membrane structure, especially the continuous arrangement of -COOH in poly(AA-co-gamma-MPS) chain. (C) 2012 Elsevier B.V. All rights reserved.