In this work, mechanical and thermal experimental techniques have been applied in order to relate the mechanical response with the microscopic variations of the material. Stress-strain results along the main directions of β-poly(vinylidene fluoride), β-PVDF, in poled and non-poled samples enables to investigate the influence of the poling process on the mechanical response of the material. Further, differential scanning calorimetry experiments allow the investigation of the effect of poling in the degree of crystallinity of the material as well as on the stability of the crystalline phase. Thermogravimetric analysis was used to investigate the kinetics of the thermal degradation of poled and non-poled β-PVDF samples. The differences observed between the two materials suggest that the poling affects the mechanical properties of the material especially in the direction parallel to the polymeric chains and originates changes at a molecular level that remain beyond the melting of the material.