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[Display omitted] • Perovskite was used for asymmetric electrocarboxylation of aromatic ketones. • 85% yield and 95% enantiomeric excess were obtained on La 0.7 Sr 0.3 Fe 0.8 Ni 0.2 O 3. • The high-performance mainly results from the increased concentration of O2– and Fe4+. • La 0.7 Sr 0.3 Fe 0.8 Ni 0.2 O 3 has enhanced intrinsic electrochemical performance. The perovskite oxides La 0.7 Sr 0.3 Fe 0.8 B 0.2 O 3 (B = Ti, Mn, Co, Ni and Cu) synthesized by sol–gel method were used as cathodes and tested in asymmetric electrocarboxylation of aromatic ketones. The study showed the La 0.7 Sr 0.3 Fe 0.8 Ni 0.2 O 3 (La7Sr3Fe8Ni2) catalyst is more active for asymmetric electrocarboxylation of acetophenone with 95% enantiomeric excess and 85% yield. The high electrocatalytic activity is attributed mainly to several factors, including the increased amount of lattice oxygen and Fe4+ species on the surface of La7Sr3Fe8Ni2, enhanced electrochemically active surface area and faster electron transfer. Furthermore, La7Sr3Fe8Ni2 also exhibited remarkable stability and reusability. [ABSTRACT FROM AUTHOR]