In the present work, a biosynthesis route for the preparation of hierarchical pompon-like SAPO-34 was developed. Commercially available bacterial cellulose aerogel was used as template. SiO2 loaded bacterial cellulose aerogel was used as silica source and a simple hydrothermal treatment was used for crystallization. XRD, FT-IR, SEM, TEM, N2 adsorption-desorption and TG techniques were employed to characterize the obtained samples. The hierarchical pompon-like SAPO-34 showed a spherical morphology that was comprised of nanosheets with a thickness less than 30 nm. The specific surface area of the hierarchical pompon-like SAPO-34 was 498 m2/g that was higher than the trigonal SAPO-34 crystals of 465 m2/g. The ultrasonic treatment experiment indicated a high stability of the pompon-like structure. In addition, the hierarchical pompon-like SAPO-34 exhibited a CO2 adsorption capacity of 2.26 mmol/g at 100 kPa and 298K and the corresponding CO2/CH4 ideal separation factor was 5.7, which was higher than that of trigonal SAPO-34 crystals. The saturated adsorption capacity and b-value were estimated using single site Langmuir, Toth and Sips adsorption isotherm models and the observed results were constant. Compared with trigonal SAPO-34, hierarchical pompon-like SAPO-34 displayed a higher saturated adsorption capacity, but a lower b-value.