The electrocatalytic reduction of carbon dioxide (CO2) is an attractive option to efficiently bind electrical energy from renewable resources in artificial carbon fuels and feedstocks. The strategy is considered as crucial part in closing the anthropogenic carbon cycle. In particular, the electrosynthetic production of Cl species such as carbon monoxide (CO) would radiate immense power, since these building blocks offer a versatile chemistry to higher carbon products and fuels. In the present study we report the exploration of the catalytic behavior of semiconducting Co3O4 nanofibers for the conversion of CO2 to CO predominantly with a Faradaic efficiency of 65%. We assist the process by expanding the electrode network with nanofibrous interconnections and hence are able to demonstrate the electrosynthesis of CO without applying any metal supplement. We use polyacrylnitrile (PAN) as template polymer to generate highly crystalline Co3O4 fibers to expand the catalytically active surface to volume ratio. The stability of the nanofibrous electrodes remains for 8 h at a geometric current density of approximately 0.5 mA/cm(2) on a flat surface. The ease of synthesis and the comparatively high Faradaic yield for CO makes Co3O4 nanofibers a potential candidate for future large scale electrode utilization.