Carbon dioxide (CO2) reduction to multi-carbon compounds at the cathode using chemolithoautotrophs is an emerging application of microbial electrosynthesis (MES). In this study, CO2 reduction in MES was investigated at hydrogen evolving potentials, separately by a mixed-culture and Clostridium ljungdahlii, using a graphite felt and stainless steel assembly as cathode. The mixed-culture reactor produced acetate at the maximum rate of 1.3 mM.d-1, along with methane and hydrogen at -1.1 V/Ag/AgCl. Over 160 days of run-time in four fed-batches, 26% of bicarbonate was converted to acetate between day 28 to 41, whereas in the late batches, methane production prevailed. Out of 45 days of run-time in the C. ljungdahlii reactor, 2.4 mM.d-1 acetate production was achieved at -0.9 V/Ag/AgCl in batch 1. Simultaneous product degradation occurred when the mixed culture was not selectively enriched. Hydrogen evolution is potentially the rapid way of transferring electrons to the biocatalysts for higher bioproduction rates.