Antimony selenide (Sb2Se3) has been widely investigated as a promising absorber material for photovoltaic devices. However, low open-circuit voltage (Voc) limits the power conversion efficiency (PCE) of Sb2Se3-based cells, largely due to the low-charge carrier density. Herein, high-quality n-type (Tellurium) Te-doped Sb2Se3 thin films were successfully prepared using a homemade target via magnetron sputtering. The Te atoms were expected to be inserted in the spacing of (Sb4Se6)n ribbons based on increased lattice parameters in this study. Moreover, the thin film was found to possess a narrow and direct band gap of approximately 1.27 eV, appropriate for harvesting the solar energy. It was found that the photoelectric performance is related to not only the quality of films but also the preferred growth orientation. The Te-Sb2Se3 film annealed at 325 °C showed a maximum photocurrent density of 1.91 mA/cm2 with a light intensity of 10.5 mW/cm2 at a bias of 1.4 V. The fast response and recovery speed confirms the great potential of these films as excellent photodetectors.