The opaque photovoltaic thermal (PVT) produces both thermal and electrical energy. In order to increase thermal energy, we have considered flexible (Al-based) photovoltaic (PV) module for the present study. Further, we have considered thermo-electric cooler (TEC) integrated with flexible PV module to enhance electrical power. As a result, an overall power can be increased in flexible PVT-TEC collector. A concept of series and parallel combination of flexible PVT-TEC collectors is proposed to optimize series (n) and parallel (m) combinations for a given number of N (=n × m) collectors for maximum overall exergy depending on thermal and electrical energies which have not been considered yet so far. Further, a new expression has also been developed for the heat removal factor and instantaneous thermal efficiency of the nth flexible PVT-TEC collector to investigate its effect on the nth flexible PVT-TEC collector performance. Numerical computations have been carried out for a given coldest climatic condition of Srinagar, India, and design parameters of Al-based PVT-TEC collectors using matlab R2021b. Based on numerical computations, the following conclusions have been drawn: (i) For case (a) (all flexible PVT-TEC collectors are connected in parallel), the daily overall exergy is 2.7 kW, which is 21.3% more than case (d). (All flexible PVT-TEC collectors are connected in series.) (ii) There is a drop of 20% in the mass flowrate factor due to the correction factor.