Utilizing a scanning photoelectron microscope (SPEM) and grazing-incidence X-ray powder diffraction (GIXRD), we studied the electronic band structure and the crystalline properties of the pentanary Cu(In,Ga)(S,Se)2 (CIGSSe) thin-film solar cell as a function of sample depth on measuring the thickness-gradient sample. A novel approach is proposed for studying the depth-dependent information on thin films, which can provide a gradient thickness and a wide cross-section of the sample by polishing process. The results exhibit that the CIGSSe absorber layer possesses four distinct stoichiometries. The growth mechanism of this distinctive compositional distribution formed by a two-stage process is described according to the thermodynamic reaction and the manufacturing process. On the basis of the depth-profiling results, the gradient profiles of the conduction and valence bands were constructed to elucidate the performance of the electrical properties (in this case, Voc = 620 mV, Jsc = 34.6 mA/cm2, and Î• = 14.04%); the valence-band maxima (VBM) measured with a SPEM in the spectroscopic mode coincide with this band-structure model, except for a lowering of the VBM observed in the surface region of the absorber layer due to the ordered defect compound (ODC). In addition, the depth-dependent texturing X-ray diffraction pattern presents the crystalline quality and the residual stress for each depth of a thin-film device. We find that the randomly oriented grains in the bottom region of the absorber layer and the different residual stress between the underlying Mo and the absorber interface, which can deteriorate the electrical performance due to peeling-off effect. An anion interstitial defect can be observed on comparing the anion concentration of the elemental distribution with crystalline composition; a few excess sulfur atoms insert in interstitial sites at the front side of the absorber layer, whereas the interstitial selenium atoms insert at the back side.