In high-temperature water (HTW), NaHCO₃ is reduced into formate using isopropanol as a reducing agent. Based on the initial reducing agent isopropanol, a relatively high yield of formate was obtained of about 70%. Another curious aspect in HTW is that water molecules may act as a catalyst for hydrogen-transfer reduction of NaHCO₃ with isopropanol, taking the place of the metal catalysts used in heterogeneous and homogeneous catalytic hydrogenation of CO₂. The present work should help facilitate studies for developing new green processes for the transformation of CO₂ using organic hydrogen sources as the reducing agents.