Pinhole-free ionic conductors are critical to achieve optimal performance in thin film-solid oxide fuel cells (TF-SOFCs). However, nanoscale defects, especially pinholes, can induce current leakage and contribute to cell failure by creating electrical short circuits. This study introduced a novel methodology for detecting pinholes in yttria-stabilized zirconia (YSZ) thin-film solid oxide electrolytes. The approach utilized selective adsorption of silver (Ag) nanoparticles generated via a spark discharge generator (SDG). Analytical techniques, including focused ion beam (FIB), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), were employed to investigate interactions between Ag nanoparticles and nanoscale defects. Results showed that nanoparticle-based diagnostic methods were efficacious for defect characterization, offering a solution for enhancing the quality of thin-film electrolytes.