Polyhydroxyalkanoates (PHAs) are biodegradable and biocompatible thermoplastics that can be synthesized in various microorganisms. Volatile fatty acids (VFAs) are produced by anaerobic treatment of organic wastes that can be utilized as inexpensive substrates for PHA synthesis. In this study, several Ralstonia eutropha strains were grown on the mixture of VFAs (acetic, propionic, and butyric acid) as its carbon and energy source for growth and PHA synthesis. R. eutropha KCTC 2658 accumulated PHAs up to 50% of dry cell weight from total 5 g/L of mixed VFAs (acetic acid : propionic acid : butyric acid=1 : 2 : 2). In batch culture of R. eutropha KCTC2658 in a 5 L fermentor, a homopolymer of poly(3-hydroxybutyrate) [P(3HB)] was produced from 20 g/L glucose as a sole carbon source with dry cell weight of 8.4 g/L and PHA content of 30%. In fed-batch culture, two feeding strategies, pulse or pH-stat, were applied to add VFAs to the fermentor. When VFAs were fed using pH-stat feeding strategy after 40 h, a copolymer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] was produced with dry cell weight of 8.1 g/L, PHA content of 50%, and 3HV fraction of 20 mol%.