The effect of Cu on highly efficient CdTe thin solid film cells with a glass/TCO/CdS/CdTe structure subjected to CdCl2 treatment was investigated by low-temperature photoluminescence (PL). The PL of the CdS/CdTe junction in samples without Cu deposition revealed a large shift in the bound exciton position due to the formation of CdSxTe1−x alloys with Eg (alloy) ≅ 1.557 eV at the interface region. After Cu deposition on the CdTe layer and subsequent heat treatment, a neutral acceptor-bound exciton (A0Cu,X) line at 1.59 eV and two additional band-edge peaks at 1.54 and 1.56 eV were observed, indicating an increase in the energy gap value in the vicinity of the CdTe/CdS interface to that characteristic of bulk CdTe. These results may suggest the disappearance of the intermixing phase at the CdTe/CdS interface due to the presence of Cu atoms in the junction area and the interaction of the Cu with sulfur atoms. Furthermore, an increase in the intensity of CdS-related peaks in Cu-doped samples was observed, implying that Cu atoms were incorporated into CdS after heat treatment.