Cu(In,Ga)Se2 (CIGS) thin films were deposited by a two-step process on Mo-coated soda-lime glass substrates. The CuInGa (CIG) precursors were prepared in an in-line evaporation system at the room temperature, and then selenised at 500 °C. The two-step processed CIGS films were mechanically compressed at 25 MPa to improve their optoelectronic properties, which were verified by photoluminescence (PL). The surface and structural properties were compared before and after compression. The mechanical compression has brought changes in the surface morphology and porosity without changing the structural properties of the material. The PL technique has been used to reveal changes in the electronic properties of the films under study. PL spectra at different excitation laser powers and temperatures were measured for as-grown as well as compressed samples. The PL spectra of the as-grown films revealed three broad and intense bands shifting at a significant rate towards higher energies (j-shift) with the increase in excitation power suggesting that the material is highly doped and compensated. At increasing temperatures, the bands shift towards lower energies, which is a characteristic of the band tails generated by spatial potential fluctuation. The compression increases the intensity of energy bands by an order of magnitude and reduces the j-shift, demonstrating an improvement of the electronic properties.