CO₂ valorization in form of synthetic natural gas is a convenient way to store large amounts of intermittent energy produced from renewable sources for long periods of time. Here reported research addresses the development of novel dual function materials (DFMs) for the utilization of CO₂ from simulated post-combustion effluent by cyclic adsorption and in-situ methanation. These DFMs, obtained after the controlled reduction of 20% La_1−xCa_xNiO₃/CeO₂-type precursors (with x = 0–0.5), are widely characterized before and after catalytic tests. XRD diffractograms, H₂-TPD experiments and STEM-EDS images denote that Ca-doping shows low influence on materials composition, slight detrimental effect on textural properties and no influence on Ni, La and Ce distribution. Meanwhile, the concentration of Ca-based species increases as long as La³⁺ substitution by Ca²⁺ increases, which leads to a progressively promotion of medium and, especially, strong basic sites concentration (CO₂-TPD). As a result, the 20% La_0.5Ca_0.5NiO₃/CeO₂-derived DFM almost doubles (188.8 µmol g⁻¹) the CH₄ production of the 20% LaNiO₃/CeO₂-derived DFM (96.5 µmol g⁻¹) at high temperatures. Indeed, this novel DFM enhances the methanation capacity of the conventional 15% Ni-15% CaO/Al₂O₃ DFM (143.0 µmol CH₄ g⁻¹), with higher stability during long-term experiments and adaptability under variable feed compositions, which further support the applicability of these novel DFMs. Thus, Ca doping emerges as an effective way of tailoring CO₂ adsorption and in-situ hydrogenation to CH₄ efficiency of 20% LaNiO₃/CeO₂-derived DFMs.