In this study, seeded zinc oxide (Z-ZnO) thin films were fabricated by a two-step electrochemical deposition process. Different annealing temperatures (300, 400, 500, and 600 °C) were investigated to determine the most effective temperature for the photocatalytic activity. Comprehensive analyses were conducted using X-Ray Diffraction (XRD), scanning electron microscopy (SEM), and UV–visible spectrophotometry. The XRD results confirmed the formation of a wurtzite hexagonal structure, with the highest crystallinity observed at 400 °C. The lowest band gap value, 3.29 eV, was also recorded for Z-ZnO thin film annealed at 400 °C. SEM images revealed that the thin film treated at 400 °C exhibited a well-defined and uniform structure, contributing to its enhanced properties. The photocatalytic efficiency of ZnO (without seeding layer) and Z-ZnO thin films annealed at 400 °C was evaluated through the degradation of tetracycline hydrochloride (TCH) to prove the effect of the presence of a primary seeding layer on ZnO 400 °C thin film efficiency. The degradation efficiency of ZnO thin film without seeding layer was 69.8%. By applying a seeding layer in Z-ZnO 400 °C thin film, the degradation efficiency has been increased to 75.8%. On the other hand, Z-ZnO 400 °C thin film achieved a high degradation efficiency of 82.6% over 300 min in the photoelectrocatalytic system. The obtained Z-ZnO thin films annealed at 400 °C are highly effective photocatalysts and photoelectrocatalysts, offering a significant potential for the degradation of pharmaceuticals and other pollutants in water.