The recently demonstrated concept to combine CO2 capture and utilization in one process using isothermal unsteady-state operation, namely CO2 capture and reduction (CCR), was applied for CO2 methanation using unpromoted and K- or La-promoted Ni/ZrO2 catalysts. Both K and La promoters significantly improve CO2 capture capacity and also the selectivity of CO2 conversion to methane. The K-promoted catalyst (Ni-K/ZrO2) captures a larger amount of CO2 at high temperature but the capture capacity drops at low temperature due to incomplete catalyst regeneration during the cyclic unsteady-state reaction condition. In contrast, the La-promoted catalyst (Ni-La/ZrO2) shows temperature-independent CO2capture capacity and rapid reduction of captured CO2, thus leading to stable CCR performance. The nature of the active sites and mechanistic details were gained by TPR, reductive CO2-TPD and space- and time-resolved operando DRIFTS, holistically elucidating the effects of the promoters and their impacts on CCR activity.