The waste heat harnessing from photovoltaic module (PV) with the thermoelectric device (TE) is considered as an ideal solution for effective thermal management of PV technologies. However, idealized operating conditions for lossless device coupling and reduction in thermal contact resistance need to be investigated further to expedite PV-TE device efficiency. Our simple approach to tandemly attach a low-cost thermoelectric cooling device (TEC) to PV module has improved its power output and electrical efficiency by 1.02% and 1.1% respectively (No. of TEC device-1, 720 W/m2 and 20 °C of water-cooling). Herein, we explored the TEC device for power production as a cost-effective alternative to the traditional thermoelectric (TEG) devices. To facilitates the facile heat transport among the PV-TEC interface, the thermal interface material (TIM) has been applied on TEC devices. The hybridized paste of nanocarbon and thermal grease (NC-TG) was used as a TIM material, morphologically evident the linear alignment between NC in TG matrix has ameliorated the uniform heat conduction. It was observed that the application of hybrid Carbon TIM materials enhances the power generation by 10.65% compared to PV-TG-TEC. The physicochemical analysis and evaluation results indicated that the low-cost synthesized hybrid carbon-based TIM material is efficient in the reduction of thermal contact resistance. Concomitantly, the high heat absorption capacity of nanocarbon accelerated the TEC performance by creating a sufficient temperature gradient across TEC ends. The present work proposed a simple and low-cost pathway for the improvement of TEC performance using hybrid carbon-based TIM material.