The effects of the modification of polyacrylonitrile ultrafiltration membranes with sodium hydroxide are discussed. The NaOH‐induced hydrolysis of nitrile groups on the membrane surface results in membranes with decreasing pore diameter. The average pore diameter changes from 2.6 to 0.6 nm in the progress of hydrolysis. The modified membranes are less prone for protein deposition. Fouling causes a pore diameter reduction of 80% for the untreated and 20% for the modified membranes. Modification results also in the creation of the membranes working in the nanofiltration mode. The unmodified membrane does not reject salt while a membrane immersed in the modification bath is capable of rejecting about 50% of calcium carbonate.