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Here, in situ assembly in La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ and CoFe 2 O 4 composite (LSCFC) cathode was induced by Pr to form La 0.6 Sr 0.4 Co x Fe y O 3-δ /PrCoO 3 /Co 3 O 4 /PrO 2 (LSCFC-PI) multiphase heterostructures. The surface of LSCFC-PI forms uniform nanoparticles, and the unique core-shell structure prevents Sr segregation, thereby enhancing CO 2 tolerance and increasing oxygen reduction reaction (ORR) active sites. Furthermore, compared with LSCFC, LSCFC-PI increases the oxygen vacancy content of the cathode due to the existence of multiphase heterostructure, improves the ORR kinetics, and the conductivity is also greatly improved. The peak power density (PPD) of LSCFC-PI as a single-cell cathode at 700 ℃ reached 1.51 W cm−2, which was 2.65 times higher than that of LSCFC's 0.57 W cm−2, and in the long-term stability test at a constant voltage ∼0.8 V for 100 hours, showing excellent stability. In situ assembly of multiphase heterostructures is expected to become a new strategy for developing high-performance IT-SOFC cathodes. [Display omitted] • Pr-induced in situ assembly of multiphase heterostructures. • Multiphase heterostructures facilitate the ORR kinetics of cathodes. • Optimize the oxygen vacancy content in multiphase structures. • LSCFC-PI has excellent ORR activity and CO 2 tolerance. [ABSTRACT FROM AUTHOR]