A thin BaZr0.7Pr0.1Y0.2O3-δ (BZPY) layer (∼3.3 μm) is fabricated on anode-supported BaCe0.8Y0.2O3-δ (BCY) electrolyte layer (∼28 μm) with pulsed laser deposition (PLD) technique. The BZPY/BCY bilayer electrolyte shows better chemical stability against CO2 atmosphere compared with the BCY single electrolyte layer. The open circuit voltages (OCVs) of 0.966, 0.997 and 1.021 V with maximum power densities of 250, 177, 122 mW cm-2 are measured in the bilayer electrolyte cell at 700, 650 and 600°C, respectively. Besides, the BZPY/BCY bilayer electrolyte cell also exhibits a good long-term stability under the operating condition. BZPY thin film deposited with PLD technique can improve chemical stability with little effect on the electrochemical performance of proton-conducting SOFC.