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The changes of substances during catalytic pyrolysis. • The structural differences of La 0.8 M 0.2 FeO 3 (M = La, Ca, Sr, Ba) are investigated. • The differences of lignin pyrolysis catalyzed by La 0.8 M 0.2 FeO 3 are compared. • The possible mechanism of lignin pyrolysis catalyzed by perovskite is proposed. A new method named the production of aryl oxygen-containing compounds via catalytic pyrolysis of bagasse lignin (BL) over perovskites, La 0.8 M 0.2 FeO 3 (M = La, Ca, Sr, Ba) was proposed. La 0.8 M 0.2 FeO 3 (M = La, Ca, Sr, Ba) samples were synthesized by the sol-gel method (SG) and characterized by XRD, SEM, BET and XPS, and their catalytic pyrolysis performances were evaluated by the test of TG and the evaluation of the fixed bed microreactor. Under the action of perovskites, the pyrolysis of BL was promoted, the yields of gaseous and solid products decreased while the yield of liquid products increased by 10–20%; decarboxylation and decarbonylation could be inhibited, and it was conducive to the fracture of aliphatic hydrocarbon side chains on aromatic rings, as a result, the selectivity of CO 2 /CO decreased while the selectivity of hydrocarbons in gaseous products increased; the total selectivity of aryl oxygen-containing compounds increased from 56 wt.% in the liquid product obtained from pure BL pyrolysis to more than 69 wt. % in that of catalytic pyrolysis of BL. The spent catalyst was regenerated after controlled combustion of solid product — char, and it showed good structural and catalytic stabilities after 5 successful redox cycles. [ABSTRACT FROM AUTHOR]