N-methylol nylon 6 membranes were prepared by reacting nylon-g with formaldehyde. Elemental analysis, used to analyze the composition of modified membranes, showed that the degree of substitution increased with formaldehyde content in the reaction solution. The modified nylon-6 membranes exhibited a high affinity to ethanol. Pervaporation results for the separation of ethanol-water mixtures showed that these membranes were water-selective, indicating that the diffusion property is the dominant factor. An N-methylol nylon-6 membrane with 33% degree of substitution showed the best membrane performance. In order to control the swelling of N-methylol nylon-6 membranes in the feed solutions of high ethanol content, thermal crosslinking was applied at 180 degrees C for different times. It was found that heat treatment of 10 minutes gave the optimal permselectivity.