Cubic AgSbTe₂ compound is a metastable phase within Ag₂Te-Sb₂Te₃ pseudo-binary phase diagram and theoretically rapid cooling molten elements to room temperature may be an effective way to obtain it. In this work, thick films composed of 5⁻10 nm fine grains were developed by a melt spinning technique. The formation mechanism of the nanostructure and its influences on the thermoelectric properties have been studied and correlated. Differential scanning calorimetry (DSC) analysis shows that the as-prepared films exhibit distinct thermodynamic properties when prepared under different cooling rates and doping element. A small amount of Se doping is effectively capable of inhibiting the emergence of the Ag₂Te impurity and optimizing the electrical transport properties. All films have positive large Seebeck coefficient, but rather small positive or negative Hall coefficient, indicating a multicarrier nature of transport consisting of both holes and electrons. A power factor of ~1.3 was achieved at 500 K for Se-doped film for its excellent electrical conductivities. This result confirms that a combination of Se doping and melting spinning technique is an effective way to obtain high phase-pure AgSbTe₂ compound and reveal its intrinsic transport properties routinely masked by impurities in sintering or slow-cooling bulk samples.