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Summary of main observation and conclusion: A series of electrospun LaCoO3 perovskites derived from CoX2 (X = CH3COO–, NO3–) were prepared and investigated for total propane oxidation. It is shown that pure rhombohedral perovskite LaCoO3 from Co(CH3COO)2 can be obtained at a relatively low temperature, 400 °C, benefitting from the complexation effect of CH3COO–. On the other hand, CH3COO– can accelerate the complete decomposition of polymer. The low‐temperature process can protect LaCoO3 nanoparticles from growing up. As a result, Co(CH3COO)2‐derived catalysts exhibit better propane oxidation activity than the ones suffered the same thermal treatment by using Co(NO3)2. XPS and H2‐TPR analysis provide that there is subtle change in Co3+/Co2+ on bulk/surface of Co(CH3COO)2‐derived catalysts prepared at different temperatures, giving rise to similar propane oxidation activities. Moreover, the result of cyclic stability test over 400 °C obtained catalyst shows little deactivation, demonstrating a good thermal stability. Our study can provide a feasible route for energy‐saving synthesis of LaCoO3 catalyst applied in the catalytic oxidation of volatile organic compounds (VOCs). [ABSTRACT FROM AUTHOR]