[en] Electronic structure evolution of LaAl_1−xCr_xO₃ (0≤ × ≤ 1) (LACO) films has been studied using x-ray photoemission spectroscopy. With increasing Al concentration, the core levels appear to systematically shift towards higher binding energy (BE). A similar trend is also observed in the BE shift for the valence band maxima (VBM). For increasing Al concentration, Cr 3d states continuously shift towards higher BE side with a progressive decrease in the Cr 3d bandwidth. We also observe interesting changes in the spectral weight and width of O 2p states for the mixed compositions (0.2 ≤ × ≤ 0.6) from the valence band fitting and difference spectra.The effects of Cr 3d band narrowing, as × decreases seem to be associated with the local distortion of the CrO₆ motifs rather than to the increase in Coulomb interactions. Furthermore, the study also reveals a band-gap engineering mechanism possible, in these LACO systems. (author)