Box Behnken design of experiment was used to study the effect of process variables such as alkali concentration, temperature and time on water retention capacity of the alkaline hydrolysed electrospun fibres. The hydrolysis of electrospun polyacrylonitrile fibres was carried out using sodium hydroxide with different processing conditions like concentration of alkali, temperature and time. With the increase in the concentration of alkali, time and temperature, the water retention capacity of membrane was found to increase in the membranes. Water retention capacities of the membranes were modeled and predicted using empirical as well as artificial neural network (ANN model). The fiber diameter and mean flow pore diameter of electrospun polyacrylonitrile fibers and hydrolyzed fibers shown in SEM images were 310 AE 50, 275 AE 75 nm, 0.9258 and 1.12 microns, respectively. The present study indicated that the nanofibrous membranes have potential for the water absorbing applications.