In this investigation, a systematic study was undertaken to measure the heat generating properties via photothermal effect of commercially available multi-crystalline silicon photovoltaic (SPV) cells while producing electricity with alternating current. For this purpose, a device was designed and fabricated with two top and bottom chambers separated by thin and highly thermal conducting metal sheet such as 0.2 mm copper sheet. For this device fabrication, 21 numbers of commercially available SPV cells were used. In order to capture the complete heat generated by the SPV cells, they were fully immersed in γ-butyrolactone, an electrochemically and thermally quite stable organic solvent, and exposed to the sunlight when its power density was about 80 mW/cm2, and the room temperature was 28 °C to 34 °C. It was found that the 21 numbers of SPV cells along with about 2 l of γ-butyrolactone upon exposure to sunlight with about 80 mW/cm2 for about 2 h during a mid-day time, the generation of about 46 °C by these materials was noted. When this heat energy was captured with dichloromethane (DCM), a low-boiling point working fluid, and sent to rotate the crack-shaft of a laboratory model commercially available reciprocally moved steam engine attached with a custom made electric generator, generated >16 V electricity with alternating current. These results are presented and discussed in this chapter.