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Summary: The enormous need for refrigeration of modern human life has inevitably aggravated the environmental crisis worldwide. To date, there are very few refrigeration technologies available beholding both harmless refrigerants and high efficiency. Here, we proposed a geothermal-thermoelectric air conditioning system (GeoTEAC) with refrigerant-free and high energy efficiency through synergistically combining the merits of thermoelectric effect and ground source heat exchanging system. The system showed competitive cooling and heating COPs of 5.83 and 2.92, respectively, with kilowatt capacity, which are 3–4 times higher than that of previously reported thermoelectric air-conditioning setups. For a conceptual scenario, we demonstrated the lowest TEWI values for the GeoTEAC system among different air-conditioning types. Our work provides sustainable and climate-friendly solutions to realize worldwide emission peaks and carbon neutralization.