Oxidative cracking is a promising process to reduce the energy and carbon intensities for light olefins production by combing catalytic oxidation and cracking reactions. This work reports an efficient redox oxidative cracking (ROC), which could avoid the potential hazard of co-feed oxygen with hydrocarbons and save the air separation process in an oxidative cracking process to achieve a much safer reaction process and more energy saving. Highly efficient redox catalysts, i.e. composites of the Li2CO3 promoted perovskite oxides (La0.8Sr0.2FeO3 and CaMnO3), were applied in ROC of naphtha by using a model compound of cyclohexane. Among the catalysts, La0.8Sr0.2FeO3@Li2CO3 exhibits excellent ROC performance (57.52 % yield of olefins and extremely low COx yield of 0.28 %), and it demonstrates high structural stability and cycling ability as well. The olefins yield in this work increased by > 19 % compared to conventional non-oxidative catalytic cracking (38 % yield of olefins), and the COx yield also decreased from 18 % to extremely low of 0.28 % compared with the best-reported O2-cofeed cyclohexane oxidative cracking. The characterization results indicated that La0.8Sr0.2FeO3@Li2CO3 attributed to being a core–shell structure with a La0.8Sr0.2FeO3 core covering with a molten Li2CO3 layer. Further characterization indicates that the modification of Li2CO3 affected the migration rate of oxygen and inhibited the excessive oxidation of olefins, which enhancing the selectivity of light olefins and inhibits COx formation. The oxygen migration rate of LSF is 5.81 × 10−11 mol/(g·s) compared with 3.37 × 10−11 mol/(g·s) of LSF@20 %Li. These findings offer a new strategy to design effective redox catalysts for redox oxidative cracking.