Vapour growth carbon nanofibres/poly(vinilidene fluoride) - VGCNF/PVDF - composites prepared by solution casting were studied. The spherulitic crystallisation morphology of the pure polymer is maintained for the composites. Mechanical stretching of the composite films induces the α to β-phase transformation within the polymer matrix. This phase transition is accompanied by the destruction of the spherulitic microstructure in favour of a microfibrillar one. The incorporation of the VGCNF in the PVDF matrix increases the degree of crystallinity of the polymer composites for concentrations lower than ∼1%, remaining stable for higher VGCNF concentrations. With respect to the electrical properties, the stretching associated to the phase transformation induces a change in the conduction mechanism: the α-phase composite demonstrates a percolative behaviour on the measured conductivity whereas the β-phase demonstrates typical ionic conduction behaviour. Dielectric measurements in conjunction with the the two exponent percolation phenomenological equation demonstrates that in the β-phase an effective reduction in the ratio VGCNF length/domain length could induce the observed percolation behaviour.