Thin films of the system (As13Te24Si27Sb18)1−xFex have been deposited by rf sputtering in argon from the powder of the corresponding composition. Structure and composition analyses have been performed using electron microscopy, electron diffraction, and electron probe x‐ray microanalysis. Using these analyses, the amorphous structure and homogeneity of the material in the films have been verified. The Fe content x varies between 0 and 0.6. Electrical transport measurements have been performed at different temperatures between 77 and 400 K for 0≤x≤0.6, and the thermoelectric power measured at room temperature. Optical reflection and transmission measurements have also been made at room temperature for several values of x. From the conductivity measurements, thermoelectric power, and optical measurements, we found that the amorphous films show metallic behavior for x≥0.4. On the basis of the above measurements, we suggest an energy‐band model which fits the experimental results.