Fossil fuels are energy recourses that fulfill most of the world’s energy requirements. However, their production and use cause severe health and environmental problems including global warming and pollution. Consequently, plant and animal-based fuels (also termed as biofuels), such as biogas, biodiesel, and many others, have been introduced as alternatives to fossil fuels. Despite the advantages of biofuels, such as being renewable, environmentally friendly, easy to source, and reducing the dependency on foreign oil, there are several drawbacks of using biofuels including high cost, and other factors discussed in the fuel vs. food debate. Therefore, it is imperative to produce novel biofuels while also developing suitable manufacturing processes that ease the aforementioned problems. Polyhydroxyalkanoates (PHAs) are structurally diverse microbial polyesters synthesized by numerous bacteria. Moreover, this structural diversity allows PHAs to readily undergo methyl esterification and to be used as biofuels, which further extends the application value of PHAs. PHA-based biofuels are similar to biodiesel except for having a high oxygen content and no nitrogen or sulfur. In this article, we review the microbial production of PHAs, biofuel production from PHAs, parameters affecting the production of fuel from PHAs, and PHAs biorefineries. In addition, future work on the production of biofuels from PHAs is also discussed.