The biomedical area in the scope of tissue regeneration pursues the development of advanced materials that can target biomimetic approaches and, ideally, have an active role in the environment they are placed in. This active role can be related to or driven by morphological, mechanical, electrical, or magnetic stimuli, among others. This work reports on the development of active biomaterials based on poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid), PHBV, a piezoelectric and biodegradable polymer, for tissue regeneration application by tailoring its morphology and functional response. PHBV films with different porosities were obtained using the solvent casting method, resorting to high-boiling-point solvents, as N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO), and the combination of chloroform (CF) and DMF for polymer dissolution. Furthermore, magnetoelectric biomaterials were obtained through the combination of the piezoelectric PHBV with magnetostrictive iron oxide (Fe3O4) nanoparticles. Independently of the morphology or filler content, all biomaterials proved to be suitable for biomedical applications.