The energy mismatch of semiconductors in the catalytic redox reactions were overcame by using triboelectric plasma. [Display omitted] • A triboelectric plasma catalytic system using metal oxide catalysts has been developed. • This system reduced CO 2 to CO at room temperature and atmospheric pressure. • TiO 2 catalyst exhibited the best activity, reaching a rate of 0.14 mmol·g cat −1·h−1, and an energy efficiency of 5.3 %. • CO 2 molecules were pre-activated to form the transient CO 2 − anions. • The limiting step of electron transfer between TiO 2 and CO 2 was avoided, overcoming the energy mismatch between catalyst and CO 2. The activities of semiconductor-based catalytic reactions are limited by mismatch between energy bandgaps of semiconductors and redox potentials of inert small molecules, especially for stable molecules, such as CO 2. Herein, a triboelectric plasma catalytic system using metal oxide catalysts has been developed, which reduces CO 2 to CO at room temperature and atmospheric pressure. Among the various metal oxide semiconductors, TiO 2 catalyst exhibited the best activity, reaching a production rate of 0.14mmol·g cat −1·h−1, and an energy efficiency of 5.3 % for the conversion of electrical to chemical energy. In triboelectric plasma, CO 2 molecules were pre-activated to form the transient CO 2 − anions, and the limiting step of electron transfer between TiO 2 and CO 2 was avoided, overcoming the energy mismatch between catalyst and CO 2. The energy barrier of CO 2 dissociation was markedly reduced to 0.18 eV. This work provides an effective strategy to overcome the energy bandgap restriction inherent in semiconductor-based catalytic reactions. [ABSTRACT FROM AUTHOR]