Oxyfuel combustion, using O2/CO2 mixed gas as the oxidant, increases CO2 concentration in the flue gas and reduces the cost of CO2 capture. Nevertheless, the cost of oxygen production is a key to make the process a viable future option. In this work, YBaCo4O7+δ (YBC114) sorbent with a layered hexagonal structure was prepared and used to produce the O2–CO2 gas mixture at a low temperature (200–400°C). YBC114 has both the ability of temperature swinging oxygen absorption/desorption (TSA) and the property of pressure swinging oxygen absorption/desorption (PSA) in the temperature range of 200–400°C. The XRD patterns show that YBC114 has a good stability in both the O2-containing and CO2-containing atmosphere at 200–400°C. Cyclic operation for the low temperature O2-enriched CO2 stream production indicates that YBC114 has high cyclic stability. The absorption/desorption kinetics can be improved by combining PSA with TSA at no cost of the O2 absorption capacity. For such a design, oxygen is absorbed when YBC114 is heated from 200°C to 345°C with a slow ramping rate in an air stream. Oxygen is desorbed and an oxygen-enriched carbon dioxide stream is obtained when YBC114 is exposed in a carbon dioxide stream and cooled from 345°C to 200°C. It has been found that the synthesis method of the YBC114 also has a significant effect on the oxygen absorption/desorption kinetics.