In this chapter, an overall view of energy matrices and embodied energy, with and without balance of system (BOS) is discussed so that the net useful electrical energy available over the life of the PV system can be evaluated. As we know that the quality of energy is more important than quantity. This chapter mainly deals with analysis of PV/T system from the point of view of first and second law of thermodynamics. The energy and exergy analysis of different PV/T solar systems, namely, air and water collector, distillation system, solar dryer, greenhouse, are discussed with results. The exergy analyses, process, exergetic analysis of PV/T systems are also presented. Solved examples are also given.