Carbon dioxide (CO2) transformation into valuable fuels and chemicals is in most cases a challenge far from readiness nowadays. One possible route for its conversion is the reverse water gas shift reaction (rWGS), crucial for syngas generation and required for the chemical conversion of CO2 to fuels and platform chemicals. In this paper, well organized Cu/Zn/Al structures were proposed as efficient catalysts for rWGS reaction at low tem-peratures. The results of in situ XRD revealed the formation of layered structures such malachite and hydro-talcite. The operando DRIFTS-MS studies of those structure suggests a participation of Cu2+/Cu+ pair in the reaction, promoting the redox mechanism and enhancing the activity at lower temperature. This work also provides a new strategy to design Cu-based rWGS catalysts able to prevent the sintering of active phase.