The state-of-the-art protonic ceramic electrolyte BaCe0.7Zr0.1Y0.1Yb0.1O3-δ (BCZYYb) dense films were successfully deposited on the pre-sintered Ni(O)+BCZYYb anode substrate by recently developed rapid laser reactive sintering (RLRS) method. The separation of the deposition of dense electrolyte from the preparation of porous anode makes it possible to manufacture protonic ceramic fuel cells (PCFCs) with more desirable electrolyte and anode microstructures. The PCFC single cells prepared after introducing the cathode thin film BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY0.1) showed OCVs of 0.94–0.97V and peak power densities of 97 mW/cm2 at 600 °C and 121 mW/cm2 at 600–650 °C under Air/H2 gradient. The proton conductivity of the BCZYYb film derived the RLRS-derived single cell showed a moderate proton conductivity of 3.7 × 10−3S/cm at 600 °C. The higher PCFC performance can be expected by further optimization of the thickness, compositions, and/or microstructures of the component layers.