Polyhydroxyalkanoates (PHAs) are polyesters that can be biologically synthesized by many microorganisms and engineered plants that have been investigated by microbiologists, biochemists, polymer scientists, material engineers, and medical researchers for several decades. Research on microbial production of PHAs has been extensively focused on using pure carbon sources, such as sugars and fatty acids. Practical considerations of production costs of PHAs have resulted in research efforts to use alternative renewable and inexpensive feedstocks. One potential feedstock for the production of PHA polymers is the glycerol waste byproduct of biodiesel production. The major focus of this review is the production of PHA polymers from glycerol. A review of biosynthetic pathways for PHAs production from glycerol, current production of waste glycerol in biodiesel industry, physical and mechanical properties of PHAs, and applications of PHAs in the areas of packaging industry, implant materials, drug carrier, biofuels, are covered. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013