The widespread application of intermediate-temperature solid oxide fuel cells is mainly being hurdled by the cathode's low efficiency on oxygen reduction reaction and poor resistance to carbon dioxide impurity. Here we report the fabrication of a hierarchical shell-covered porous cathode through infiltration followed by microwave plasma treatment. The hierarchical shell consists of a dense thin-film substrate with cones on the top of the substrate, leading to a three-dimensional (3D) heterostructured electrode. The shell allows the cathode working stably in CO2-containing air, and significantly improving the cathode's oxygen reduction reactivity with an area specific resistance of ∼0.13 Ωcm2 at 575°C. The method is also suitable for fabricating functional shell on the irregularly shaped substrate in various applications.