An opaque photovoltaic combined with thermoelectric cooler (PV-TEC) collector is presented in this chapter, in which a TEC module is incorporated at the base of a PV module to improve the overall electrical efficiency of the system. A mathematical model has been described with photovoltaic combined thermoelectric cooler with a duct of air and this thermal modeling is used to calculate the thermal and electrical energy gain. On an annual basis, weather data is received from IMD Pune for the month of May. Several types of temperatures such as solar cells, thermoelectric cooler top side, thermoelectric cooler bottom side, duct outlet temperatures have been calculated through the thermal modeling developed for the system. These results show overall electrical efficiency with TEC increasing by 10.34-12.01%. The addition of a thermoelectric module with a photovoltaic module increases the electrical power from 6.93176 W-15.6753 W to 7.64854 W-17.5571 W. The thermal energy gain by the photovoltaic-thermoelectric module along the duct is in the range of 7.89134 W-20.7169 W. © 2023 Nova Science Publishers, Inc.