Ferulic acid esterases (FAEs) act synergistically with xylanases to hydrolyze the feruloylated decorations of the hemicellulosic fraction of cell wall material and therefore play a major role in the degradation of plant biomass. In this review, their role in plant biomass degradation, their production, classification, and structural determination are discussed. In addition, the production, physicochemical properties, and molecular biology of the different type of FAEs are presented, giving emphasis in their potential applications utilizing their hydrolytic and synthetic activity. A detailed map of the reaction systems used to date is demonstrated, underpinning the potential of these enzymes as biosynthetic tools in the synthesis of bioactive compounds for use in food and cosmeceutical industries.