Measurements of electronic structure, microstructure and thermoelectric properties of zinc antimonide thin films prepared by direct current magnetron co-sputtering were carried out. The as-deposited zinc antimonide thin film had a very high resistivity similar to insulating ceramics, which was due to a low binding energy of both zinc and antimony, with the electron scattering increases and impedes the current transport. With the increase in annealing temperature, the films became more crystalline and the thermoelectric properties were also improved. The resistivity of the film decreased rapidly with its crystallinity when the annealing temperature was above 350 °C. The Seebeck coefficients of the thin films were positive, indicating that the films were P-type. The Seebeck coefficient of those samples increased with increasing annealing temperature. The thin film annealed at 400 °C has an optimal power factor of 1.87 × 10⁻³ Wm⁻¹ K⁻² with a Seebeck coefficient of 300 μVK⁻¹ and a resistivity of 4.82 × 10⁻⁵ Ωm at 573 K.