We have demonstrated vertically aligned poly(vinylidene fluoride)(PVDF) nanorods fabricated by a 200nm-diameter porous template technique. Their shape and physical properties were controlled by finding an appropriate solvent in casting solutions. In this study, the effect of the solvent on the PVDF nanostructures was investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR) and piezoresponse force microscopy (PFM). Importantly, the rheological properties of the PVDF solutions strongly influenced both diameter and length of the nanorods. Additionally, the dipole moments and evaporation rate of solvents affected the formation of ferroelectric β phase in the PVDF nanorods, which was confirmed by XRD, FTIR and PFM. This offers our rationale for a great promise in energy harvesters scavenging energy from mechanical vibration sources.