The synthetic SDW exhibited good potential as a substrate for VFA production. After 21 days of fermentation in batch vessels fed with F/M of 1.6–6.4 gCOD/gVSS and an initial alkalinity of 1.0–2.5 gCaCO3/L, an average of 59.4 ± 9.2% of the initial COD of SDW was converted into VFA. In all cases, at least two-thirds of the conversion occurred during the first 6 days. The main products of the fermentation process of the synthetic SDW were HAc (34 ± 12%) and n-HBu (44 ± 16%). The experimental conditions, which did not include any external source of inhibition for methanogenic activity, did not completely prevent VFA consumption. However, feedingwith an F/M ratio of 4.0 gCOD/gVSS or higher avoided the consumption of VFA in 73% of the cases. The ranges of F/M and alkalinity that were studied generated a relevant range of pH values and the pH affected both the TVFA production and the VFA composition. Compared to acidic pH values (3.9–5.2), neutral and low-alkaline pH values (6.5–7.8) enhanced VFA production and generated a more diversified VFA composition on average.