Poly(vinylidene fluoride) (PVDF) and its copolymers are the polymers with the highest dielectric constants and electroactive responses, including piezoelectric, pyroelectric and ferroelectric effects. This semicrystalline polymer can crystallize in five different forms, each related to a different chain conformation. Of these different phases, the β phase is the one with the highest dipolar moment and the highest piezoelectric response; therefore, it is the most interesting for a diverse range of applications. Thus, a variety of processing methods have been developed to induce the formation of the polymer β phase. In addition, PVDF has the advantage of being easily processable, flexible and low-cost. In this protocol, we present a number of reproducible and effective methods to produce β-PVDF-based morphologies/structures in the form of dense films, porous films, 3D scaffolds, patterned structures, fibers and spheres. These structures can be fabricated by different processing techniques, including doctor blade, spin coating, printing technologies, non-solvent-induced phase separation (NIPS), temperature-induced phase separation (TIPS), solvent-casting particulate leaching, solvent-casting using a 3D nylon template, freeze extraction with a 3D poly(vinyl alcohol) (PVA) template, replica molding, and electrospinning or electrospray, with the fabrication method depending on the desired characteristics of the structure. The developed electroactive structures have shown potential to be used in a wide range of applications, including the formation of sensors and actuators, in biomedicine, for energy generation and storage, and as filtration membranes.