In the context of carbon neutrality, the phase-out of coal from the energy structure has resulted in numerous old coal mines that possess abundant underground space resources suitable for underground pumped hydroelectric energy storage (UPHES). Site selection and estimation of potential are critical to the planning and implementation of UPHES in old coal mines. This paper introduces a two-step site selection concept, including a screening assessment followed by a comprehensive assessment, to determine suitable locations for UPHES. The screening indicators in the screening assessment comprise geological features, mine water disasters, and minimum installed capacity, while the analytic hierarchy process (AHP) is applied in the comprehensive assessment. Additionally, coal mines in Henan Province are preliminarily screened through the screening assessment and the potential for UPHES is thoroughly investigated. The estimated volume of the drifts and shafts in old coal mines is approximately 1.35 × 107 m3, while in producing coal mines, it is around 2.96 × 107 m3. Furthermore, the corresponding annual potential for UPHES is 1468.9 GWh and 3226.3 GWh, respectively. By consuming surplus wind and solar power, UPHES is able to reduce 4.68 × 105 tonnes of carbon dioxide (CO2) emissions. The study provides preliminary guidance for policy-makers in developing UPHES in old coal mines.