Te nanowires made from stabilizer-depleted CdTe nanoparticles are assembled in thin films following a layer-by-layer assembly protocol. The thin film has a distinctively metallic mirror-like appearance and displays a strong photoconductance effect characteristic of narrow-bandgap semiconductors. In situ reduction of gold results in the formation of An nanoparticles adhering to Te nanowires, which leads to the disappearance of photoconductivity of the Te thin film.