The CO2 catalytic reduction activities of four different Co-modified Ni-based catalysts derived from hydrotalcite-like materials (HTCs) prepared by co-precipitation method were investigated under thermal and photocatalytic conditions. All catalysts were tested from 473 to 723 K at 10 bar (abs). The light intensity for photocatalytic reactions was 2.4 W cm-2. The samples were characterized to determine the effect of morphological and physicochemical properties of mono-bimetallic active phases on their methanation activity. The activity toward CO2 methanation followed the next order: Ni > Co–Ni > Co. For the monometallic Ni catalyst an increase of a 72% was achieved in the photo-catalytic activity under UV and vis light irradiation at temperatures lower by > 100 K than those in a conventional reaction. Co-modified Ni based hydrotalcite catalysts performed with stability and no deactivation for the 16 h studied under visible light for methanation at 523 K due to the presence of basic sites. ; This research was supported by: Basque Government Project: IT1554-22 and University of the Basque Country. Grant PID2020-112889RB-I00 funded by: MCIN/AEI/10.13039/501100011033. Authors are grateful for the support provided: SGIker/UPV/EHU & European funding (ERDF and ESF).