After giving a glimpse into the global market of bioplastics and briefly describing the various forms of bioplastics, this chapter presents a detailed discussion on polyhydroxybutyrate (PHB), the predominant polyhydroxyalkanoate produced by bacteria as stored food. This review encompasses interdependent sections on the organization of the PHB granules, their physical properties, factors affecting production, producing bacteria, genetic basis of production, overproduction using recombinant techniques, metabolic pathways, blends, general applications, degradation and conclusions. To sum up, a collective and global initiative of scientists, law makers and entrepreneurs is required to enhance the present market share of bioplastics from a mere 1% to a state where bioplastics replace petroplastics completely in the near future. However, considering the small share of PHB in total bioplastics, and its unique characteristics, it is advisable that PHB research should focus on developing biomedical devices for tissue and organ engineering; cosmetics and health products; food packaging materials; and delivery systems for the controlled release of drugs, fertilizers and pesticides.