Poly(3-hydroxybutyrate-
co
-3-hydroxyvalerate), PHBV, is a microbial biopolymer with excellent biocompatible and biodegradable properties that make it a potential candidate for substituting petroleum-derived polymers. However, it lacks mechanical strength, water sorption and diffusion, electrical and/or thermal properties, antimicrobial activity, wettability, biological properties, and porosity, among others, limiting its application. For this reason, many researchers around the world are currently working on how to overcome the drawbacks of this promising material. This review summarises the main advances achieved in this field so far, addressing most of the chemical and physical strategies to modify PHBV and placing particular emphasis on the combination of PHBV with other materials from a variety of different structures and properties, such as other polymers, natural fibres, carbon nanomaterials, nanocellulose, nanoclays, and nanometals, producing a wide range of composite biomaterials with increased potential applications. Finally, the most important methods to fabricate porous PHBV scaffolds for tissue engineering applications are presented. Even though great advances have been achieved so far, much research needs to be conducted still, in order to find new alternative enhancement strategies able to produce advanced PHBV-based materials able to overcome many of these challenges.