The present work aimed to study the performance of ultrafiltration (UF) membranes for hemicelluloses separation, from a caustic-containing highly alkaline, cellulose purification solvent stream of viscose rayon production process, and to understand the membrane behaviour, effect of multiple use cycle, identify potential performance drawbacks and propose possible solutions. Screening experiments showed that an UF membrane with a nominal molecular weight cut-off value of 3 kDa can be used to separate hemicelluloses from alkaline process stream. UF membrane was found to be prone to performance deterioration with time due to fouling. Higher feed temperature helped in improving the membrane flux values while maintaining hemicelluloses retention.