Photovoltaics is a promising technology to produce sustainable energy, thanks to the high amount of energy emitted by the sun. One way of having solar cells with low production costs is to apply thin-film technology and with earth-abundant raw materials. A keen interest is arising in kesterite compounds, which are chalcogenides composed of abundant and non-toxic elements. They have already achieved excellent performance at the laboratory level. Here, we report the synthesis and characterization of mixed chalcogenides based on copper, zinc, iron, and tin. Solutions have been studied with different zinc and iron ratios. The distortion of the elementary cell of kesterite increases with the addition of iron until a phase transition to stannite occurs. The process of synthesis and deposition proposed herein is cheap and straightforward, based on the sol-gel technique. These thin films are particularly attractive for use in cheap and easily processable solar cells. The synthesized layers have been characterized by X-ray diffraction, UV-Vis absorption, and Raman, X-ray photoelectron, and energy-dispersive X-ray spectroscopy measurements.