This work presents a novel and sustainable solution based on combined heat and power (CHP) system integrated with a simultaneous charging-discharging type thermal energy storage tank. The multi-generation system uses biogas as the heat source and is analyzed from the thermodynamic, exergoeconomic, and environmental perspectives. The proposed configuration aims to meet the electrical requirements of a cluster of 20 villages, greenhouse heating, and hot air production for agricultural drying applications. The exhaust gases from the biogas fired turbine are utilized to power a recompression supercritical CO2 and steam Rankine cycle. The additional surplus heat is stored inside a simultaneous charging/discharging type thermal storage tank that provides favorable conditions (50–55 °C) for biogas producing microorganisms to maximizing gas production. The meso-erythritol (sugar alcohol) is used as a phase change material due to its high latent heat and large supercooling (>60 °C), suitable for the present applications. The PCM is characterized on heat flux Differential scanning calorimeter (DSC) and thermophysical properties are evaluated. Further, the exergoeconomic analysis is presented to examine the economic viability of the system which serves as a holistic solution for rural power generation. It is found that the total product unit cost of the system is 12.96 $/GJ and operating charges are 140.5 $/h. The proposed multigenerational system promises a Levelized cost of electricity at 5 ¢ /kWh. The net overall electricity generated by the system is 1432 kW and provides 200 kW of space thermal heating. In addition, hot air is produced at the rate of 9720 kg/h for different agricultural drying applications.