Hydrogenation of CO2 to hydrocarbons is one of the crucial technologies to address the energy deficit and increasing environmental pollution. In this work, we have synthesized and systematically studied the influence of composition and nanostructure of a Fe-based, carbon-coated core–shell nanocatalyst. The synthesis method offered good control over the thickness of the carbon coating in the core–shell catalyst, which in turn controlled the chemical composition of the core. The results emphasized an optimal amount of Fe3O4, Fe5C2 in the core and partially graphitized carbon in the shell for a high catalytic activity in the conversion of CO2 at atmospheric pressure with higher selectivity to C2-C4 olefins. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim