The effect of solar cell processing (including etching in KCN along with deposition of CdS and ZnO) on photoluminescence (PL) spectra and bandgap Eg (measured at 4.2 K by photoluminescence excitation) of Cu2ZnSnSe4 films, produced by selenising metallic precursors at 450 °C, 500 °C and 550 °C, was studied. Temperature and excitation intensity analysis of the P1 dominant band in the PL spectra of solar cells suggests that after processing this band still can be assigned to the free-to-bound recombination of free electrons with holes bound at deep acceptor levels influenced by valence band-tails. However processing increased the intensity of P1 and blue shifted it. The strongest effect was observed for the film selenised at 500 °C. For the film selenised at 450 °C the blue shift and increase in the intensity were smaller and only a slight intensity rise was found for the film selenised at 550 °C. The intensity increase we assign to a reduction in the concentration of non-radiative recombination centers on the surface because of the etching and changes in doping due to inter-diffusion of Cd, S, Se and Zn after the deposition of CdS. Such an inter-diffusion depends on the elemental composition of the films defining the chemistry of defects and influencing Eg which increased in the film selenised at 500 °C but decreased in the other films. Processing increased the P1 shift rate (j-shift) with excitation power change in all the films demonstrating a higher compensation degree in the solar cells which is consistent with the formation of an interface layer containing new donors CdCu.