β-poly(vinylidene fluoride) - β-PVDF - exhibits ferroelectric properties due to the special arrangement of the chain units in the crystalline phase. The ferroelectric phase can be optimised by poling the original stretched film, that tends to align the randomly organised crystallites against the applied field. In this work, polarised and non-polarised β-PVDF from the same batch are characterised by mechanical tests and a series of thermal analysis techniques, including DMA, TMA and DSC. The films exhibit mechanical anisotropy, and in the longitudinal direction the poled film presents larger mechanical properties, due to the higher structural organisation. Poled and non-poled show similar crystallinity levels but the melting temperature probed by DSC is higher for the non-poled film; for both films the melting peak exhibits a complex shape, indicating a heterogeneous crystalline organization. Two relaxation processes were found (β and αc) by dynamic mechanical analysis (DMA). The β process, attributed to segmental motions in the amorphous phase, appears at the same temperature in both directions, but its intensity was found to be higher for the films tested in the longitudinal direction. For a given direction, the poled films exhibit lower peaks, due to the more organised amorphous structure. At higher temperature, the αc-relaxation was related to the contraction of the films in the longitudinal direction during heating, recorded by thermal mechanical analysis (TMA). The onset of molecular mobility within the crystalline phase allows for cooperative diffusion processes in the amorphous phase, generating the randomisation of the initially oriented structure. © 2004 Published by Elsevier B.V.