Working temperature-dependent photovoltaic and optoelectronic properties of FTO/TiO2/SnS/Ag solar cell are presented using the Raman spectroscopy and electrical characterizations. Nanostructured SnS thin film is deposited using a green binder by the spin coating method. The effect of addition of the CdS layer is also investigated on the temperature-dependence of the mentioned properties. Raman results indicate that addition of the CdS layer increases the induced strain on the solar cell. An increase in the working temperature decreases the photovoltaic performances of solar cells due to different factors. Mobility (μh) and trap-filled limit voltage (VTFL) of solar cells are increased and decreased by increasing the temperature, respectively. Finally, the results obtained in this study demonstrate the key role of the working temperature in the photovoltaic and optoelectronic behavior of the SnS solar cell, which can be used to understand this behavior in the other third generation of solar cell materials.