This work studies the pH effect in xylose mixed culture fermentation, focusing on lactic and butyric acid production. Batch tests showed a complete substrate consumption at slightly acidic (pH 6) and alkaline conditions (pH 8), but a great inhibition of xylose conversion was observed at pH 4. Acetic acid was the only product at pH 8, while at pH 6, butyric and propionic acids were quantified as well with a large proportion of unidentified compounds. Continuous reactor operation showed that changes within the acidic pH range (pH 4.5 to pH 6) affect the acidification degree but not the product distribution, reaching the maximum butyric acid yield (0.38 Cmol/Cmol-s) at pH 5, while lactic acid was only detected when xylose conversion or butyric acid concentration dropped. Batch tests demonstrated that butyric acid was not inhibitory for xylose or lactic acid conversion and that the main product of lactic acid fermentation was butyric acid. Although pH is an essential variable steering the fermentation yield and selectivity, this study demonstrates that it must be combined with other operational conditions in order to obtain a stable production of lactic and butyric acids.