Cellulose triacetate (CTA) polymer among cellulose esters were used for preparing hollow fiber membranes by phase separation method to investigate the gas permeation properties. To endow gas separation properties, 1,4-dioxane and LiCl were used as additives in the polymer dope solution. The spinning conditions including spinning temperature were controlled to form an active skin layer on the hollow fiber surface. Scanning electron microscopy was used to examine morphology of surface and cross section of the prepared CTA hollow fibers. The gas permeation performance of CTA hollow fiber membranes showed $P_{CO2}$ = 17 GPU and ${alpha}_{CO2/N2}$ = 48.