Removing toxic formaldehyde (HCHO) from environmental water is crucial for human health and the ecosystem. Perovskite-type Lanthanum cobalt oxide (LaCoO₃) has achieved great success in a wide range of catalytic processes; however, this concept has been rarely applied to the degradation of HCHO. Here, we prepared perovskite-type catalysts with different La/Co molar ratios, and the time for HCHO oxidation degradation at room temperature was shortened by 12 times (10 min vs. 119 min) compared to other heterogeneous catalysts. LaCoO₃ exhibits superior catalytic activity for HCHO degradation at room temperature when the La/Co molar ratio is 1:1 compared to lanthanum cobalt oxides with other molar ratios. The X-ray photoelectron spectroscopy (XPS) test results show that increasing the La/Co molar ratio reduces the Co²⁺ content in the catalyst, while Co²⁺ plays the most important role in the catalyst. Quencher experiments indicated that sulfate radicals (SO₄·⁻) and hydroxyl radicals (·OH) were the primary reactive species for the removal of HCHO. This finding suggests that the catalytic oxidation reaction involving HCHO operates as a heterogeneous Fenton-like oxidation reaction.