Thermally rearranged poly(benzoxazole-co-amide) (TR-PBOA) copolymer membranes were prepared by treating poly(o-hydroxyamide-co-amide) (PHAA) precursors by in-situ thermal cyclization reaction for the H-2 separation at high temperature. The physical properties, membrane processability and gas permeation property can be controlled by varying the ratio of diamine compounds. The rigid biphenyl moiety in the copolymer membranes increases gas selectivity whereas the flexible ether moiety improves membrane processability as well as gas permeability. Moreover, thermal rearrangement process affects the gas separation properties of TR copolymer membranes. TR polymer membranes derived from polyhydroxyamides (PHAs) demonstrated high H-2 permeability, but low H-2/CO2 selectivity. However, TR-PBOA copolymer membranes improved H-2/CO2 selectivity. Both permeability and selectivity of H-2 over CO2 increased due to the high activation energy for H-2 permeation through the copolymer membranes and can be explained by thermodynamic theory with temperature. The highest performance was 26.8 Barrer of H-2 permeability and 8.0 of H-2/CO2 selectivity measured at 210 degrees C. (C) 2013 Elsevier B.V. All rights reserved