Amorphous alloys are a promising alternative to Pd alloy membranes for hydrogen separation because of their lower cost and comparable hydrogen permeability. A series of amorphous alloy membranes consisting of Ni60Nb20Zr20 (at%), (Ni0.6Nb0.4)100−xZrx and (Ni0.6Nb0.3Ta0.1)100−xZrx (where x=0, 10, 20 or 30) were prepared by melt spinning and then coating the foil surfaces with a thin (500nm) layer of Pd using physical vapor deposition (PVD). A (Ni0.6Nb0.4)70Zr30 membrane exhibited the highest hydrogen permeability (1.4×10−8molm−1s−1Pa−0.5) of any of the materials, measured in pure hydrogen at 450°C. Membrane permeability increased with Zr content, but membranes higher in Zr were more susceptible to brittle failure and were more thermally unstable. Decreases in hydrogen permeability were almost always observed during long-term permeability tests at 400 and 450°C. The addition of Ta slightly increased the thermal stability, but moderately lowered the hydrogen permeability. An AES depth profile of the membrane surface showed that metallic interdiffusion had taken place between the Pd coating and the bulk membrane, which probably accounts for the reduction in hydrogen permeability over time at 400–450°C.