<P><B>Abstract</B></P> <P>The hydrogenation of carbon dioxide offers a large range of possible reactions for converting hydrogen to chemical compounds that can be easily stored, transported and used as fuels or platform molecules. In this study, CO<SUB>2</SUB> hydrogenation was biocatalysed by multispecies microbial communities to produce formate, butyrate and acetate. A hybrid metal/microbial catalysis was pointed out in the presence of iron. Addition of FeCl<SUB>3</SUB> 10 mM increased the production of acetate by 265% and butyrate by 73%, to 5.26 and 14.19 g/L, respectively. A stable acetate production rate of 830 mg/L/d was thus sustained for more than 20 days. The presence of iron promoted the selection of Firmicutes and the best performances were linked to the growth of a restricted number of dominant species of two genera: <I>Clostridium</I> and <I>Megasphaera</I>. Various possible catalysis mechanisms are discussed and guidelines are proposed for further development and scale-up of the process.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Multispecies microbial consortia catalyse CO<SUB>2</SUB> hydrogenation. </LI> <LI> Iron ions at a few mM concentration considerably enhanced the microbial catalysis. </LI> <LI> Both the final concentration of the products and the production rates were increased. </LI> <LI> High production rate was sustained for weeks without product extraction or pH control. </LI> <LI> Iron enhanced the selection of the two microbial genera <I>Clostridium</I> and <I>Megasphaera.</I> </LI> </UL> </P>