An anaerobic granular sludge was enriched to utilize H2/CO2 in a continuous gas-fed up-flow anaerobic sludge reactor by applying operating conditions expected to produce acetic acid, butyric acid and ethanol. Three stages of fermentation were found: Stage I with acetic acid accumulation with the highest concentration of 35 mM along with a pH decrease from initial 6 to 4.5. In Stage II, H2/CO2 was replaced by 100% H2 to induce solventogenesis, whereas butyric acid was produced with the highest concentration of 2.5 mM. At Stage III with 10 μM tungsten (W) addition, iso-valeric acid, valeric acid and caproic acid were produced at pH 4.5 -5.0. In the batch tests inoculated with the enriched sludge taken from the bioreactor (day 70), however, methane production occurred at pH 6. Exogenous 15 mM acetate addition enhanced both the H2 and CO2 consumption rate compared to exogenous 10, 30 and 45 mM acetate by the enriched sludge. Exogenous acetate failed to be converted to ethanol using H2 as electron donor by the enriched acetogens.