Volatile fatty acids (VFAs) were produced from the marine macroalgae, Laminaria japonica, Pachymeniopsis elliptica, and Enteromorpha crinite by anaerobic fermentation using a microbial community derived from a municipal wastewater treatment plant. Methanogen inhibitor (iodoform), pH control, substrate concentration, and alkaline and thermal pretreatments affected VFA productivity. Acetic, propionic, and butyric acids were the main products. A maximum VFA concentration of 15.2 g/L was obtained from 50 g/L of L. japonica in three days at 35 degrees C and pH 6.5-7.0. Pretreatment with 0.5 N NaOH improved VFA productivity by 56% compared to control. The result shows the applicability of marine macroalgae as biomass feedstock for the production of VFAs which can be converted to mixed alcohol fuels. (C) 2012 Elsevier Ltd. All rights reserved.