Atmosphere plasma spray and robot digital fabricating were integrated and presented to prepare the planar PEN and MOLB-type PEN SOFCs. On the basis of the spraying conditions optimized previously and the self-developed functionally graded powder feed system, two kinds of PEN cells were prepared. Then the microstructure and material components of the PEN cells were analyzed. The results show that graded layers were formed between the electrodes and electrolyte. Moreover, the material components and the porosity of the graded layers vary gradually. In particular, the porosities of the anode and cathode reach 32.74%, 32.24%, respectively. Using the AC complex impedance technology, the conductivity of the MOLB-type composite electrode is tested. As a comparison, the electrical conductivity of the MOLB-type composite electrode with the graded layers is larger than that without the graded layers.