Display omitted •Highly efficient Mo2C catalysts for CO2 conversion via RWGS•Cu as a promoter boost the CO2 conversion due to higher active sites concentration.•Cs is an excellent dopant to enhance CO selectivity, especially at low temperatures.•Electronic interactions and re-carburisation accounting for Cs positive effect•Robust catalysts for long term operations. Mo2C is an effective catalyst for chemical CO2 upgrading via reverse water-gas shift (RWGS). In this work, we demonstrate that the activity and selectivity of this system can be boosted by the addition of promoters such as Cu and Cs. The addition of Cu incorporates extra active sites such as Cu+ and Cu° which are essential for the reaction. Cs is an underexplored dopant whose marked electropositive character generates electronic perturbations on the catalyst’s surface leading to enhanced catalytic performance. Also, the Cs-doped catalyst seems to be in-situ activated due to a re-carburization phenomenon which results in fairly stable catalysts for continuous operations. Overall, this work showcases a strategy to design highly efficient catalysts based on promoted β-Mo2C for CO2 recycling via RWGS.