The aim of this study is synthesis of polyurethane (PU) composites from 4,4 '-methylenebis(cyclohexyl isocyanate), 1,2-ethanediol and different amounts of copper-based polyoxometalate (Cu-POM) and investigation of their dielectric properties. Firstly, Cu-POM structure as reinforcement was synthesized with ammonium heptamolybdate and Cu metal ion salt by a hydrothermal synthesis method. Then, Cu-POM-PU composites were prepared by in situ polymerization process. The prepared Cu-POM-PU composites were characterized by means of various techniques for their structure, morphology and thermal behaviour. The chemical structure, surface and morphological properties of the obtained composites were studied by Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) techniques. Thermal properties of these Cu-POM-PU composites were determined by thermogravimetric analysis, differential thermal analysis and differential scanning calorimetry analysis techniques. Dielectric properties of the Cu-POM-PU composites were also determined. The dielectric measured results showed that the dielectric constants decreased with the increase of the Cu-POMs content. The Cu-POM-PU composites showed relatively low dielectric constant compared to pure PUs.