Abstract Highest ratio of separation area to volume of membranes can be achieved by the use of hollow fiber configuration. Ceramic hollow fibers with outer diameters no larger than 1 mm are used as supports for dense Pd membranes. Pd layers of 2–3 μm thick are deposited by electroless plating technique. H 2 permeances are 7–10 m 3/m 2 h bar at 350–450 °C. The durability in H 2 is tested at 430 °C for 800 h. H 2 permeance keeps over 10 m 3/m 2 h bar and the separation factor of H 2/N 2 over 1000, which shows the possibilities to be applied in H 2 separation and catalysis at high temperatures.