Livelihood improvement in the rural areas is the key parameters to achieve the Sustainable Development Goals. This paper attempts the livelihood improvement in rural areas through green energy technologies. The manuscript comprises a detailed review of electric vehicles with unique features of micro cold storage and vehicle-to-grid technologies. A critical analysis of the intrinsic properties of thermoelectric cooler-based micro cold storage for better material selection, performance, and optimization techniques for effective electric vehicle integration is reported. The manuscript encapsulates the thermoelectric intrinsic parameters like Seebeck coefficient (S), electrical conductivity (σ), thermal conductivity (K), and figure of merit (ZT) parameters with coefficient of performance and cooling capacity (QC) for different types of thermoelectric modules. The review narrows down into suitable parameters for effective combined system design, such as optimal operating voltage (Vopt) and current (Iopt). The manuscript further reviewed and presented the V2G-enabled nanogrid, control, and grid integration techniques for better-integrated operation. This paper reported an experimental investigation on the designed and developed green agro storage integrated V2G enabled nano grid for a rural village in India. The case analysis was carried out by short distance agro produce transportation, decentralized DC–DC control, and phase-locked loop grid synchronization technique. The electrical, thermal and dynamic system characteristics study was carried out and reported. Also, the manuscript highlights the potential strengths, challenges, opportunities and research gaps for the stakeholders to build a sustainable future. The proposed combined system design will pave a sustainable pathway for achieving sustainable development goals.