In the present study, we provide useful data related to one of the most promising materials in thin-film solar cell technologies: Cu2ZnSnS4 (CZTS) kesterite structures. Sol-gel spin coating and chemical bath deposition methods were used to fabricate and further investigate Mo/CZTS/CdS/ZnO/AZO heterostructures. In order to examine the crystal structure of the samples, Raman scattering measurements using two excitation wavelengths (514.5 nm and 785 nm) were performed. Three Raman bands related to CZTS were found, as well as one that had its origin in CdS. By using laser ablation and performing Raman spectroscopy on these modified samples, it was shown that during the manufacturing process a MoS2 interlayer was formed between the CZTS and Mo layers. Our method proved that the CZTS layer in a multilayer device structure fabricated by solution-based methods can be decomposed, and thus a detailed analysis of the layer can be performed. Subsequently, current-voltage curves were investigated in terms of the essential electrical properties of glass/Mo/p-CZTS/n-CdS/ZnO/AZO junctions and occurring current transport mechanisms. Finally, AFM data were acquired to study the surface topography of the studied samples. The images showed that these surfaces had a uniform grain structure.