Biomass chemical looping gasification (BCLG) is a promising technology utilizes lattice oxygen for partial oxidation to produce high-value fuels. But in the field of BCLG, oxygen uncoupling chemical looping gasification (OU-CLG) is a novel concept that introduces molecular oxygen to optimize traditional gas-solid reactions. In this work, based on the most representative oxygen uncoupling elements successfully doped into La-Fe-O oxygen carriers, the results showed that the reaction performance not be positively correlated with the degree of oxygen uncoupling, only Co doping exhibited a better gasification performance than LaFeO3 did. Further, Co-LF differs from conventional LF in that it performs better in ex-situ gasification than in-situ gasification, with a total gas yield and carbon conversion efficiency of 1078.70 ml/g and 75.15% respectively. Further characterizations revealed that Co doping led to changes in the physical structure and reducibility. More importantly, enriched lattice oxygen and oxygen vacancies induced the formation of disordered reactive oxygen species in perovskite lattice, which promote the further oxygen uncoupling and the formation of oxygen uncoupling vacancies in ex-situ gasification. Moreover, doped but failure to promote the CLG might due to oxygen scarcity, impurity and elemental catalytic properties. Finally, a clear reaction mechanism regarding OU-CLG was proposed.