Thin sputter-deposited silver films were oxidized anodically in 1 M NaOH. The structural modifications of the silver electrode surface during the course of a complete oxidation/reduction cycle were studied in situ with the grazing incidence X-ray absorption fine structure technique. The results show that the short-range order structure of the anodic oxide films is similar to that of crystalline Ag2O powder at 0.6 V while it resembles the structure of crystalline AgO at 0.85 V (SHE). Besides a significantly reduced reflectivity, the metal surface revealed a more disordered near-order structure after a completed oxidation/reduction cycle.