The problem of CO2 mitigation on a small and medium scale can be resolved by developing a combined system of CO2 capture and its consecutive conversion into valuable products. The first stage of CO2 looping, however, should be reliable, effective and easy to control and radiofrequency heating, as a new advanced technology, can be used to improve the process. CO2 absorption and desorption RF units can be installed within power plants and powered during the periods of low energy demand thus stabilizing the electrical grid. In this work, a CaO sorbent produced by template synthesis was studied as a sorbent for a CO2 looping system under RF heating which offers short start-up times, highly controlled operation, high degree of robustness and low price. The sorbent reached its stable CO2 capacity of 15.4 wt.% already after 10 temperature cycles (650/850 degrees C) under RF heating. Higher CO2 desorption rate and lower degree of the sorbent sintering was observed under RF heating as compared to conventional heating.