We report on a cobalt/manganese-oxide interface catalyst with outstanding activity and selectivity towards methane even at high temperatures and ambient pressure in CO2 hydrogenation. The catalyst was formed from a MnCo2O4-based spinel structure during the oxidative-reductive pretreatment process just before the catalytic tests. Several Mn-, Fe- and Ni-containing cobaltite spinel and reverse spinel structures were tested to find the best overall performer. The reusable MnCo2O4-based structure featured a CO2 consumption rate of similar to 8500 nmol*g(-1)*s(-1). Even though methane is not the thermodynamically favoured product, it was produced with similar to 80% and similar to 50% selectivity at ambient pressure at 673 K and 823 K, respectively. This unexpected finding is linked to the presence of a unique nanostructured Co/Mn(II)O catalyst with a surface composition of Mn3.3Co2.0O4.7 formed after the pretreatment activation step. Over this phase, the reduction of CO2 progresses through bridge bonded formate located at the Co/Mn2+ interface and this is mostly responsible for high temperature methane formation. This hypothesis is proven here by the reported combination of ex-situ XRD, TPR, HRTEM-ED, HAADF-EDX and in-situ NAP-XPS and DRIFTS techniques. (C) 2020 The Authors. Published by Elsevier Inc.