Perovskite oxides are versatile materials due to their wide variety of compositions offering promising catalytic properties, especially in oxidation reactions. In the presented study, LaFe1−xCoxO3 perovskites were synthesized by hydroxycarbonate precursor co-precipitation and thermal decomposition thereof. Precursor and calcined materials were studied by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TG), and X-ray powder diffraction (XRD). The calcined catalysts were in addition studied by transmission electron microscopy (TEM) and N2 physisorption. The obtained perovskites were applied as catalysts in transient CO oxidation, and in operando studies of CO oxidation in diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). A pronounced increase in activity was already observed by incorporating 5% cobalt into the structure, which continued, though not linearly, at higher loadings. This could be most likely due to the enhanced redox properties as inferred by H2-temperature programmed reduction (H2-TPR). Catalysts with higher Co contents showing higher activities suffered less from surface deactivation related to carbonate poisoning. Despite the similarity in the crystalline structures upon Co incorporation, we observed a different promotion or suppression of various carbonate-related bands, which could indicate different surface properties of the catalysts, subsequently resulting in the observed non-linear CO oxidation activity trend at higher Co contents.