. In this paper, thin palladium (Pd) membranes, which are supported on alumina nanofiber nonwoven produced by electrospinning method, were prepared by electroless plating method. The influence of different pretreatment methods (iron wire activation) and reducing agent (sodium hypophosphite and hydrazine hydrate) on the structure of Pd membrane were studied. The morphology, surface element and crystal structure of the Pd membrane were investigated by SEM, EDS and XRD. The results showed that the compact Pd membrane was formed on the alumina nanofiber nonwoven when the pretreatment method of iron wire activation was adopted and the reducing agent of sodium hypophosphite was used, which will be applied widely in hydrogen separation area.