The La2(Ce0.3Zr0.7)2O7-3wt%Y2O3 coating was deposited by electron beam physical vapor deposition (EB-PVD). In order to reveal the structure evolution of the coating with the deposition parameter, the selected rotation rates of the substrate were 0rpm, 5, 15 and 25rpm, while the substrate temperature was fixed at 870°C based on the structure zone model of 0.3<Tsub/Tmp<0.5. The microstructure of the column tips ranged from a ‘triangular pyramid’ (branch tips at 5rpm and column tips at 0rpm) to a ‘roof top’, then to a ‘pyramid’ with increasing the rotation rate. Under stationary deposition, the columnar crystals grew along the <110> direction. The tips of the ‘roof top’ or the pyramids were covered by four {111} planes. During rotation deposition, the columnar crystal grew along the <100> direction. If one assumes that the pore fraction has little effect on the thermal conductivity, the ‘C’ shaped Type I pores reduced the thermal conductivity, the straight Type I pores increased the thermal conductivity, the lamellar Type II pores significantly reduced the thermal conductivity. The minimum thermal conductivity was 0.761W/(mK) at the rotation rate of 15rpm. This gives an approach to optimize the structure of the La2(Ce0.3Zr0.7)2O7-3wt%Y2O3 coatings.