Even though skeletal muscle cells can naturally regenerate as a response to insignificant tissue damages, more severe injuries can cause irreversible loss of muscle cells mass and/or function. Until now, cell therapies are not a good approach to treat those injuries. Biomaterials such as poly(vinylidene fluoride), PVDF, can improve muscle regeneration by presenting physical cues to muscle cells that mimic the natural regeneration environment. In this way, the ferroelectric and piezoelectric properties of PVDF offer new opportunities for skeletal muscle tissue engineering once the piezoelectricity is an electromechanical effect that can be used to provide electrical signals to the cells, upon mechanical solicitations, similar to the ones found in several body tissues. Thus, previous to dynamic experiments, it is important to determine how the surface properties of the material, both in terms of the poling state (positive or negative net surface charge) and of the morphology (films or fibers) influence myoblast differentiation. It was observed that PVDF promotes myogenic differentiation of C2C12 cells as evidenced by quantitative analysis of myotube fusion, maturation index, length, diameter and number. Charged surfaces improve the fusion of muscle cells into differentiated myotubes, as demonstrated by fusion and maturation index values higher than the control samples. Finally, the use of random and oriented beta-PVDF electrospun fibers scaffolds has revealed differences in cell morphology. Contrary to the randomly oriented fibers, oriented PVDF electrospun fibers have promoted the alignment of the cells. It is thus demonstrated that the use of this electroactive polymer represents a suitable approach for the development of electroactive microenvironments for effective muscle tissue engineering.