The paper introduces Ti₂₆Ni₂₁V₅₃ alloy membrane as a potential replacement for Pd-based membrane. The pressure–temperature–hydrogen permeation relationships of Pd-coated Ti₂₆Ni₂₁V₅₃ alloy membrane have been investigated under pure hydrogen and mixed hydrogen gas with carbon dioxide and carbon monoxide in a pressure range from 0.5 to 2 atm over a wide temperature range including the typical hydrogen membrane operating temperature range (350–450 °C). The experiments show that the hydrogen flux was directly proportional to the temperature at constant pressure according to an Arrhenius-type relationship, whereas it was not proportional to the square root of hydrogen partial pressure in little accordance with the Sievert's law. The hydrogen permeability values obtained for the Pd-coated Ti₂₆Ni₂₁V₅₃ alloy membrane under present conditions are higher than the pure palladium and those previously published in the Ti–Ni–V ternary systems.