The permeation properties of Nafion (R) at 35 degrees C are presented for pure gases H-2, N-2, O-2, CH4, CO2, C2H6 and C3H8, as a function of pressure between 2 and 20 atm. The effect of pressure on permeability and selectivity is analyzed to understand two observed phenomena: compression and plasticization. In pure gas experiments, at increasing feed pressure, compression of the polymer matrix reduced the permeability of low-sorbing penetrants H-2, N-2, O-2, and CH4. In contrast, permeabilities of more soluble penetrants CO2 and C2H6 increased by 18% and 46% respectively, as plasticization effects overcame compression effects. Permeability of C3H8 decreased slightly with increasing pressure up to 4.6 atm as a result of compression, then increased by 3-fold at 9 atm as a result of plasticization associated with high C3H8 solubility. Binary CO2/CH4 (50:50) mixed-gas experiments at total feed pressures up to 36 atm quantified the effect of CO2 plasticization on separation performance. At 10 atm CO2 partial pressure, CH4 permeability increased by 23% relative to its pure-gas value of 0.078 Barrer, while CO2 permeability decreased by 28%. Consequently, CO2/CH4 selectivity decreased to 19, i.e., 42% below its pure-gas value of 32. (C) 2016 Elsevier B.V. All rights reserved.