The special channels and intrinsic defects within GO laminates make it a very potential candidate for gas separation in recent years. Herein, the gas separation performance of GO membranes prepared on the surface of ceramicα-Al_2O_3 hollow fibre was investigated systematically. The microstructures of ceramic hollow fibre supported GO membranes were optimized by adjusting operation conditions. And, the GO membrane fabricated at 30 min exhibited great promising H_2 recovery ability from H_2/CO_2 mixture. At room temperature, the H_2 permeance was over 1.00 × 10~(-7)mol·m~(-2)·s~(-1)·Pa~(-1)for both single gas and binary mixture. The corresponding ideal selectivity and mixture separation factor reached around 15 and 10, respectively. In addition, humility, operation temperature, H_2 concentration in the feed and the reproducibility were also studied in this work. The special channels and intrinsic defects within GO laminates make it a very potential candidate for gas separation in recent years. Herein, the gas separation performance of GO membranes prepared on the surface of ceramic α-Al 2 O 3 hollow fiber was investigated systematically. The microstructures of ceramic hollow And, the GO membrane fabricated at 30 min showed great promising H_2 recovery ability from H_2 / CO_2 mixture. At room temperature, the H 2 permeance was over 1.00 × 10 ~ (-7) mol · M ~ (-2) · s ~ (-1) · Pa ~ (-1) for both single gas and binary mixture. The corresponding ideal and mixture separation factor reached around 15 and 10, respectively. In addition, humility, operation temperature, H_2 concentration in the feed and the reproducibility were also studied in this work.