Using an improved microemulsion process novel ZnO nanostructures can be prepared on a large scale. These radial ZnO nanowires grow on hexagonal prism tips and form nanowire clusters. A detailed study of variations in dielectric properties dependent on frequency and temperature shows that composites of radial ZnO and PVDF have significantly higher dielectric constants and exhibit better thermal stability than bulk ZnO/PVDF composites as well as showing a low percolation threshold. Already a low content of radial ZnO increases the dielectric constant of the polymer matrix significantly to a value above. 100.