Tb3+-doped CaNb2O6 (CaNb2O6:Tb3+) thin films were deposited on quartz substrates at a growth temperature of 300 °C using radio-frequency magnetron sputtering. The deposited thin films were annealed at several annealing temperatures for 20 min and characterized for their structural, morphological, and luminescent properties. The experimental results showed that the annealing temperature had a significant effect on the properties of the CaNb2O6:Tb3+ thin films. The crystalline structure of the as-grown CaNb2O6:Tb3+ thin films transformed from amorphous to crystalline after annealing at temperatures greater than or equal to 700 °C. The emission spectra of the thin films under excitation at 251 nm exhibited a dominant emission band at 546 nm arising from the 5D4 → 7F5 magnetic dipole transition of Tb3+ and three weak emission bands at 489, 586, and 620 nm, respectively. The intensity of the 5D4 → 7F5 (546 nm) magnetic dipole transition was greater than that of the 5D4 → 7F6 (489 nm) electrical dipole transition, indicating that the Tb3+ ions in the host crystal were located at sites with inversion symmetry. The average transmittance at wavelengths of 370~1,100 nm decreased from 86.8 % at 700 °C to 80.5 % at an annealing temperature of 1,000 °C, and a red shift was observed in the bandgap energy with increasing annealing temperature. These results suggest that the annealing temperature plays a crucial role in developing green light-emitting CaNb2O6:Tb3+ thin films for application in electroluminescent displays.