Carbon molecular sieve (CMS) membranes with rigid and uniform pore structures are ideal candidates for high temperature- and pressure-demanded separations, such as hydrogen purification from the steam methane reforming process. Here, we report a facile and scalable method for the fabrication of cellulose-based asymmetric carbon hollow fiber membranes (CHFMs) with ultramicropores of 3–4 Å for superior H 2 separation. The membrane fabrication process does not require complex pretreatments to avoid pore collapse before the carbonization of cellulose precursors. A H 2 /CO 2 selectivity of 83.9 at 130 °C (H 2 /N 2 selectivity of >800, H 2 /CH 4 selectivity of >5700) demonstrates that the membrane provides a precise cutoff to discriminate between small gas molecules (H 2 ) and larger gas molecules. In addition, the membrane exhibits superior mixed gas separation performances combined with water vapor- and high pressure-resistant stability. The present approach for the fabrication of high-performance CMS membranes derived from cellulose precursors opens a new avenue for H 2 -related separations.