Background: In times of global climate change, the conversion and capturing of inorganic CO 2 have gained increased attention because of its great potential as sustainable feedstock in the production of biofuels and biochemicals. CO 2 is not only the substrate for the production of value-added chemicals in CO 2-based bioprocesses, it can also be directly hydrated to formic acid, a so-called liquid organic hydrogen carrier (LOHC), by chemical and biological catalysts. Recently, a new group of enzymes were discovered in the two acetogenic bacteria Acetobacterium woodii and Thermoanaerobacter kivui which catalyze the direct hydrogenation of CO 2 to formic acid with exceptional high rates, the hydrogen-dependent CO 2 reductases (HDCRs). Since these enzymes are promising biocatalysts for the capturing of CO 2 and the storage of molecular hydrogen in form of formic acid, we designed a whole-cell approach for T. kivui to take advantage of using whole cells from a thermophilic organism as H 2 /CO 2 storage platform. Additionally, T. kivui cells were used as microbial cell factories for the production of formic acid from syngas. Results: This study demonstrates the efficient whole-cell biocatalysis for the conversion of H 2 + CO 2 to formic acid in the presence of bicarbonate by T. kivui. Interestingly, the addition of KHCO 3 not only stimulated formate formation dramatically but it also completely abolished unwanted side product formation (acetate) under these conditions and bicarbonate was shown to inhibit the membrane-bound ATP synthase. Cell suspensions reached specific formate production rates of 234 mmol g −1 protein h −1 (152 mmol g −1 CDW h −1), the highest rates ever reported in closed-batch conditions. The volumetric formate production rate was 270 mmol L −1 h −1 at 4 mg mL −1. Additionally, this study is the first demonstration that syngas can be converted exclusively to formate using an acetogenic bacterium and high titers up to 130 mM of formate were reached. Conclusions: The thermophilic acetogenic bacterium T. kivui is an efficient biocatalyst which makes this organism a promising candidate for future biotechnological applications in hydrogen storage, CO 2 capturing and syngas conversion to formate.