The efficiency of solid oxide fuel cell cathodes can be improved by microstructural optimization and using active layers, such as doped bismuth oxides. In this work, Bi1.5Y0.5O3 (BYO) films are prepared by spray-pyrolysis deposition at reduced temperatures on a Zr0.84Y0.16O1.92 (YSZ) electrolyte. The influence of the BYO film on the performance of an La0.8Sr0.2MnO3 (LSM) cathode prepared by traditional screen-printing and spray-pyrolysis is investigated. A complete structural, morphological, and electrochemical characterization is carried out by X-ray diffraction, electron microscopy, and impedance spectroscopy. The incorporation of BYO films decreases the Area Specific Resistance (ASR) of screen-printed cathodes from 6.4 to 2.2 Ω cm2 at 650 °C. However, further improvements are observed for the nanostructured electrodes prepared by spray-pyrolysis with ASRs of 0.55 and 1.15 Ω cm2 at 650 °C for cathodes with and without an active layer, respectively. These results demonstrate that microstructural control using optimized fabrication methods is desirable to obtain high-efficiency electrodes for solid oxide fuel cell (SOFC) applications.